Copolymers and terpolymers based on chlorotrifluoroethylene and vinyl chloride and use thereof
阅读说明：本技术 基于三氟氯乙烯和氯乙烯的共聚物和三元共聚物及其用途 (Copolymers and terpolymers based on chlorotrifluoroethylene and vinyl chloride and use thereof ) 是由 陆长清 帕斯卡尔·博洛梅 拉吉夫·拉特纳·辛格 保罗·托达罗 于 2018-05-12 设计创作，主要内容包括：本发明公开了用于膜、涂层、阻挡膜和其他应用中的具有改善的特性,并且具体地讲高玻璃化转变温度的三氟氯乙烯和氯乙烯的共聚物和三元共聚物,以及用于形成此类共聚物和三元共聚物的方法,所述共聚物和三元共聚物可用于反渗透脱盐、纳滤、超滤、微滤、膜蒸馏、渗透蒸发、选择性气体分离、电池和燃料电池。(Copolymers and terpolymers of chlorotrifluoroethylene and vinyl chloride with improved properties, and in particular high glass transition temperatures, for use in membranes, coatings, barrier films and other applications, and methods for forming such copolymers and terpolymers, which are useful for reverse osmosis desalination, nanofiltration, ultrafiltration, microfiltration, membrane distillation, pervaporation, selective gas separation, batteries and fuel cells are disclosed.)
1. A copolymer of Chlorotrifluoroethylene (CTFE) and Vinyl Chloride (VC), the copolymer consisting essentially of chlorotrifluoroethylene monomer units and vinyl chloride monomer units, the copolymer having a Tg of about 70 ℃ to about 87 ℃.
2. The copolymer of claim 1, comprising:
(i) from about 5% to about 50% by weight of chlorotrifluoroethylene monomer units, and
(ii) about 50 wt% to about 95 wt% vinyl chloride monomer units.
3. The copolymer of claim 2, wherein the copolymer has a surface energy of about 30mJ/m2 to about 40mJ/m2, a Tg of about 75 ℃ to about 87 ℃, and a weight average molecular weight of about 100,000 daltons to about 300,000 daltons.
4. The copolymer of claim 4, wherein the copolymer has a surface energy of about 32mJ/m2 to about 38mJ/m 2.
5. The copolymer of claim 4 having a weight average molecular weight of about 140,000 daltons to about 250,000 daltons.
6. A terpolymer of Chlorotrifluoroethylene (CTFE) and Vinyl Chloride (VC) and Maleic Acid (MA), said terpolymer consisting essentially of chlorotrifluoroethylene monomer units, vinyl chloride monomer units and maleic acid monomer units, said copolymer having a Tg of about 75 ℃ to about 87 ℃.
7. The terpolymer of claim 5 comprising:
(i) from about 5% to about 50% by weight of chlorotrifluoroethylene monomer units,
(ii) about 50 wt% to about 95 wt% vinyl chloride monomer units, and
(iii) about 15 wt% or less maleic acid monomer units.
8. The terpolymer of claim 8 wherein the copolymer has a surface energy of about 30mJ/m2 to about 40mJ/m2, a Tg of about 75 ℃ to about 87 ℃, and a weight average molecular weight of about 100,000 daltons to about 300,000 daltons.
9. A method of preparing a copolymer or terpolymer comprising Chlorotrifluoroethylene (CTFE) monomer units and Vinyl Chloride (VC) monomer units and optionally one or more third monomer units, the method comprising:
(a) providing an initial reaction medium comprising CTFE monomer and VC monomer in a CTFE to VC weight ratio of about 50:50 to about 5: 95; and
(b) reacting the CTFE monomer and the VC monomer under conditions to produce a copolymer or terpolymer comprising VC monomer units, the weight percentage of the VC monomer units (based on the total weight of the copolymer or terpolymer produced) being within 10% of the weight of the VC monomer in the initial reaction medium.
10. The method of claim 8, wherein the reacting step comprises introducing the CTFE monomer and the VC monomer to the reaction medium under conditions to produce a copolymer or terpolymer comprising VC monomer units, the weight percent of VC monomer units (based on the total weight of the copolymer or terpolymer produced) being within 2% of the weight percent of VC monomer introduced to the reaction medium (based on the total monomer introduced to the reaction medium).
11. The method of claim 9, wherein the conditions comprise conducting the reaction at a temperature in the range of about 20C to about 50C for a period of at least about 15 hours to produce a copolymer having a glass transition temperature of about 75 ℃ to about 87 ℃, a weight average molecular weight of about 100,000 daltons to about 300,000 daltons, and a surface energy of about 32mJ/m2 to about 38mJ/m 2.
Technical Field
The present technology relates to copolymers and terpolymers based on chlorotrifluoroethylene and vinyl chloride monomers and their synthesis, composition, properties and uses.
Background
Polychlorotrifluoroethylene (PCTFE) is a semi-crystalline polymer having high transparency to visible light and excellent moisture resistance and oxygen barrier properties. PCTFE also has good chemical and thermal stability. However, PCTFE is insoluble in commonly used organic solvents, which hinders the use of PCTFE in many applications, such as coatings and films. Polyvinyl chloride (PVC) is a low cost plastic polymer with good chemical stability but is brittle. Plasticizers are needed to improve the flexibility and processability of PVC.
Chlorotrifluoroethylene (CTFE) has been copolymerized with different comonomers, such as ethylene and vinylidene fluoride, to obtain corresponding copolymers having the desired characteristics. Chlorotrifluoroethylene (CTFE) and Vinyl Chloride (VC) copolymers are one of these CTFE-based copolymers. However, the applicant has realised that existing CTFE/VC copolymers have certain disadvantages.
In U.S. Pat. No. 2,915,506, a Chlorotrifluoroethylene (CTFE)/vinylidene fluoride (VDF)/Vinyl Chloride (VC) terpolymer is disclosed. The presence of vinyl chloride in the terpolymer facilitates ease of crosslinking or vulcanization to a degree not obtainable when dealing with copolymers of chlorotrifluoroethylene and vinylidene fluoride alone. However, the synthesis and composition of chlorotrifluoroethylene/vinyl chloride copolymers is not concerned.
U.S. Pat. No. 4,515,927 discloses a process for the suspension polymerization of vinyl chloride and chlorotrifluoroethylene. The objective of the process disclosed in the' 927 patent is to produce a copolymer having a relatively constant weight ratio of about 75 to 95 weight percent vinyl chloride and 5 to 25 weight percent chlorotrifluoroethylene, the weight ratio being independent of conversion. The' 927 patent discloses that vinyl chloride is known to be more reactive than chlorotrifluoroethylene, so that vinyl chloride tends to react more rapidly and the monomer mixture quickly becomes depleted of vinyl chloride. Thus, existing processes, including the process of the' 927 patent, use techniques for adding vinyl chloride in a stepwise manner to reconstitute the initial ratio of vinyl chloride to chlorotrifluoroethylene feed with a change in the weight ratio of vinyl chloride to chlorotrifluoroethylene in the copolymer before the conversion is reached. In the process of the' 927 patent, the process begins with an initial charge of vinyl chloride in the reactor, and then, after initiation of the polymerization reaction, additional vinyl chloride is added in a total of 2 to 5 stages in an amount sufficient to copolymerize 1 to 20 weight percent of the unreacted monomers prior to the next addition of vinyl chloride (see examples 2-7). For example, the process of example 5 of the' 927 patent utilizes a five-stage VC addition process and achieves an overall copolymer yield of 81.2%, and produces a copolymer having a VC/CTFE weight ratio of 80/20, a molecular weight of 66,300, and a glass transition temperature (Tg) of about 33 ℃.
U.S. patent No. 4,702,961 discloses a method of melt processing a stabilized vinyl chloride/chlorotrifluoroethylene copolymer using an organometallic stabilizer using a method as disclosed in the' 927 patent.
The applicant has found that the existing processes for the preparation of VC/CTFE copolymers produce polymeric materials having certain drawbacks. For example, copolymers prepared according to the teachings of the' 927 patent have a molecular weight of less than about 70,000 and a glass transition temperature of about 33 ℃ to 34 ℃. Applicants have found that novel copolymers of VC and CTFE can be prepared which have much higher molecular weights and glass transition temperatures than copolymers prepared by the prior process of the' 927 patent. Furthermore, applicants have found that the higher molecular weight and higher Tg copolymers prepared by the present invention have significant and important advantages in many applications compared to copolymers of VC and CTFE prepared by prior methods.
Disclosure of Invention
The present invention comprises copolymers of Chlorotrifluoroethylene (CTFE) and Vinyl Chloride (VC) which have advantageous properties, and in particular relatively high glass transition temperatures and/or high molecular weights.
The present invention includes copolymers of Chlorotrifluoroethylene (CTFE) and Vinyl Chloride (VC) consisting essentially of chlorotrifluoroethylene monomer units and vinyl chloride monomer units, the copolymers having a Tg of about 70 ℃ to about 87 ℃. For convenience, the copolymer according to this paragraph is sometimes referred to herein as copolymer 1. This property is measured by DSC Q200 instrument (TA) at a temperature rise of 10 ℃/min for the glass transition temperature as described herein (see B.Wanderlich, Thermal Analysis, Academic Press,1990, p.417-431 (B.Wanderlich, Thermal Analysis, Academic Press,1990, pp. 417-431).
As used herein, the term "chlorotrifluoroethylene monomer units" refers to the polymer fraction formed by the polymerization of CTFE.
As used herein, the term "vinyl chloride monomer unit" refers to the polymer portion formed by the polymerization of VC.
The present invention includes copolymers of Chlorotrifluoroethylene (CTFE) and Vinyl Chloride (VC) consisting essentially of chlorotrifluoroethylene monomer units and vinyl chloride monomer units, the copolymers having a Tg of about 75 ℃ to about 87 ℃. For convenience, the copolymer according to this paragraph is sometimes referred to herein as copolymer 2.
The present invention includes copolymers of Chlorotrifluoroethylene (CTFE) and Vinyl Chloride (VC) consisting of chlorotrifluoroethylene monomer units and vinyl chloride monomer units, the copolymers having a Tg of about 70 ℃ to about 87 ℃. For convenience, the copolymer according to this paragraph is sometimes referred to herein as copolymer 3.
The present invention includes copolymers of Chlorotrifluoroethylene (CTFE) and Vinyl Chloride (VC) consisting of chlorotrifluoroethylene monomer units and vinyl chloride monomer units, the copolymers having a Tg of about 75 ℃ to about 87 ℃. For convenience, the copolymer according to this paragraph is sometimes referred to herein as copolymer 4.
The present invention includes copolymers of Chlorotrifluoroethylene (CTFE) and Vinyl Chloride (VC) consisting essentially of chlorotrifluoroethylene monomer units and vinyl chloride monomer units, the copolymers having a Tg of about 70 ℃ to about 87 ℃, a molecular weight of about 100,000 to about 300,000, and a surface energy of about 30mJ/m2 to about 40mJ/m 2. For convenience, the copolymer according to this paragraph is sometimes referred to herein as copolymer 5. With respect to molecular weight as described herein, this property refers to the weight average molecular weight as measured by gel permeation chromatography as described in detail herein. In terms of surface energy, this property is measured by water and diiodomethane contact angle measurements as described in detail below.
The present invention includes copolymers of Chlorotrifluoroethylene (CTFE) and Vinyl Chloride (VC) consisting essentially of chlorotrifluoroethylene monomer units and vinyl chloride monomer units, the copolymers having a Tg of about 70 ℃ to about 87 ℃, a molecular weight of about 140,000 to about 250,000, and a surface energy of about 30mJ/m2 to about 40mJ/m 2. For convenience, the copolymer according to this paragraph is sometimes referred to herein as copolymer 6.
The present invention includes copolymers of Chlorotrifluoroethylene (CTFE) and Vinyl Chloride (VC) consisting essentially of chlorotrifluoroethylene monomer units and vinyl chloride monomer units, the copolymers having a Tg of about 75 ℃ to about 87 ℃, a molecular weight of about 140,000 to about 250,000, and a surface energy of about 32mJ/m2 to about 38mJ/m 2. For convenience, the copolymer according to this paragraph is sometimes referred to herein as copolymer 7.
The present invention includes copolymers of Chlorotrifluoroethylene (CTFE) and Vinyl Chloride (VC) consisting of chlorotrifluoroethylene monomer units and vinyl chloride monomer units, the copolymers having a Tg of about 70 ℃ to about 87 ℃, a molecular weight of about 100,000 to about 300,000, and a surface energy of about 30mJ/m2 to about 40mJ/m 2. For convenience, the copolymer according to this paragraph is sometimes referred to herein as copolymer 8.
The present invention includes copolymers of Chlorotrifluoroethylene (CTFE) and Vinyl Chloride (VC) consisting of chlorotrifluoroethylene monomer units and vinyl chloride monomer units, the copolymers having a Tg of about 70 ℃ to about 87 ℃, a molecular weight of about 140,000 to about 250,000, and a surface energy of about 30mJ/m2 to about 40mJ/m 2. For convenience, the copolymer according to this paragraph is sometimes referred to herein as copolymer 9.
The present invention includes copolymers of Chlorotrifluoroethylene (CTFE) and Vinyl Chloride (VC) consisting of chlorotrifluoroethylene monomer units and vinyl chloride monomer units, the copolymers having a Tg of about 75 ℃ to about 87 ℃, a molecular weight of about 140,000 to about 250,000, and a surface energy of about 32mJ/m2 to about 38mJ/m 2. For convenience, the copolymer according to this paragraph is sometimes referred to herein as copolymer 10.
The present invention includes a copolymer of Chlorotrifluoroethylene (CTFE) and Vinyl Chloride (VC) consisting essentially of from about 5 wt% to about 50 wt% chlorotrifluoroethylene monomer units and from about 50 wt% to about 95 wt% vinyl chloride monomer units, the copolymer having a Tg of from about 70 ℃ to about 87 ℃. For convenience, the copolymer according to this paragraph is sometimes referred to herein as copolymer 11.
The present invention includes a copolymer of Chlorotrifluoroethylene (CTFE) and Vinyl Chloride (VC) consisting essentially of from about 5 wt% to about 50 wt% chlorotrifluoroethylene monomer units and from about 50 wt% to about 95 wt% vinyl chloride monomer units, the copolymer having a Tg of from about 75 ℃ to about 87 ℃. For convenience, the copolymer according to this paragraph is sometimes referred to herein as copolymer 12.
The present invention includes a copolymer of Chlorotrifluoroethylene (CTFE) and Vinyl Chloride (VC) consisting essentially of from about 5 wt% to about 50 wt% chlorotrifluoroethylene monomer units and from about 50 wt% to about 95 wt% vinyl chloride monomer units, the copolymer having a Tg of from about 70 ℃ to about 87 ℃, a molecular weight of from about 140,000 to about 250,000 and a surface energy of from about 32mJ/m2 to about 38mJ/m 2. For convenience, the copolymer according to this paragraph is sometimes referred to herein as copolymer 13.
The present invention includes a copolymer of Chlorotrifluoroethylene (CTFE) and Vinyl Chloride (VC) consisting essentially of from about 5 wt% to about 50 wt% chlorotrifluoroethylene monomer units and from about 50 wt% to about 95 wt% vinyl chloride monomer units, the copolymer having a Tg of from about 75 ℃ to about 87 ℃, a molecular weight of from about 140,000 to about 250,000 and a surface energy of from about 32mJ/m2 to about 38mJ/m 2. For convenience, the copolymer according to this paragraph is sometimes referred to herein as copolymer 14.
The present invention includes copolymers of Chlorotrifluoroethylene (CTFE) and Vinyl Chloride (VC) consisting of from about 5 wt% to about 50 wt% chlorotrifluoroethylene monomer units and from about 50 wt% to about 95 wt% vinyl chloride monomer units, the copolymers having a Tg of from about 70 ℃ to about 87 ℃. For convenience, the copolymer according to this paragraph is sometimes referred to herein as copolymer 15.
The present invention includes copolymers of Chlorotrifluoroethylene (CTFE) and Vinyl Chloride (VC) consisting of from about 5 wt% to about 50 wt% chlorotrifluoroethylene monomer units and from about 50 wt% to about 95 wt% vinyl chloride monomer units, the copolymers having a Tg of from about 75 ℃ to about 87 ℃. For convenience, the copolymer according to this paragraph is sometimes referred to herein as copolymer 16.
The present invention includes a copolymer of Chlorotrifluoroethylene (CTFE) and Vinyl Chloride (VC) consisting of about 5 wt% to about 50 wt% chlorotrifluoroethylene monomer units and about 50 wt% to about 95 wt% vinyl chloride monomer units, the copolymer having a Tg of about 70 ℃ to about 87 ℃, a molecular weight of about 140,000 to about 250,000 and a surface energy of about 32mJ/m2 to about 38mJ/m 2. For convenience, the copolymer according to this paragraph is sometimes referred to herein as copolymer 17.
The present invention includes a copolymer of Chlorotrifluoroethylene (CTFE) and Vinyl Chloride (VC) consisting of about 5 wt% to about 50 wt% chlorotrifluoroethylene monomer units and about 50 wt% to about 95 wt% vinyl chloride monomer units, the copolymer having a Tg of about 75 ℃ to about 87 ℃, a molecular weight of about 140,000 to about 250,000 and a surface energy of about 32mJ/m2 to about 38mJ/m 2. For convenience, the copolymer according to this paragraph is sometimes referred to herein as copolymer 18.
The present invention includes a terpolymer of Chlorotrifluoroethylene (CTFE), Vinyl Chloride (VC), and maleic acid consisting essentially of chlorotrifluoroethylene monomer units, vinyl chloride monomer units, and maleic acid units, the copolymer having a Tg of about 70 ℃ to about 87 ℃. For convenience, the terpolymer according to this paragraph is sometimes referred to herein as terpolymer 1.
As used herein, the term "maleic acid monomer unit" refers to the portion of the polymer formed by polymerization of maleic acid or other units in the terpolymer that produce maleic acid moieties (such as maleic anhydride).
The present invention includes a terpolymer of Chlorotrifluoroethylene (CTFE), Vinyl Chloride (VC), and Maleic Acid (MA) consisting essentially of chlorotrifluoroethylene monomer units, vinyl chloride monomer units, and maleic acid monomer units, the copolymer having a Tg of about 75 ℃ to about 87 ℃. For convenience, the terpolymer according to this paragraph is sometimes referred to herein as terpolymer 2.
The present invention includes a terpolymer of Chlorotrifluoroethylene (CTFE), Vinyl Chloride (VC), and maleic acid consisting essentially of chlorotrifluoroethylene monomer units, vinyl chloride monomer units, and maleic acid monomer units, the copolymer having a Tg of about 70 ℃ to about 87 ℃. For convenience, the terpolymer according to this paragraph is sometimes referred to herein as terpolymer 3.
The present invention includes a terpolymer of Chlorotrifluoroethylene (CTFE), Vinyl Chloride (VC), and maleic acid consisting essentially of chlorotrifluoroethylene monomer units, vinyl chloride monomer units, and maleic acid monomer units, the copolymer having a Tg of about 75 ℃ to about 87 ℃. For convenience, the terpolymer according to this paragraph is sometimes referred to herein as terpolymer 4.
The present invention includes a terpolymer of Chlorotrifluoroethylene (CTFE), Vinyl Chloride (VC), and maleic acid consisting essentially of chlorotrifluoroethylene monomer units, vinyl chloride monomer units, and maleic acid monomer units, the copolymer having a Tg of about 70 ℃ to about 87 ℃, a molecular weight of about 100,000 to about 300,000, and a surface energy of about 30mJ/m2 to about 40mJ/m 2. For convenience, the terpolymer according to this paragraph is sometimes referred to herein as terpolymer 5.
The present invention includes a terpolymer of Chlorotrifluoroethylene (CTFE), Vinyl Chloride (VC), and maleic acid consisting essentially of chlorotrifluoroethylene monomer units, vinyl chloride monomer units, and maleic acid monomer units, the copolymer having a Tg of about 70 ℃ to about 87 ℃, a molecular weight of about 140,000 to about 250,000, and a surface energy of about 30mJ/m2 to about 40mJ/m 2. For convenience, the terpolymer according to this paragraph is sometimes referred to herein as terpolymer 6.
The present invention includes a terpolymer of Chlorotrifluoroethylene (CTFE), Vinyl Chloride (VC), and maleic acid consisting essentially of chlorotrifluoroethylene monomer units, vinyl chloride monomer units, and maleic acid monomer units, the copolymer having a Tg of about 75 ℃ to about 87 ℃, a molecular weight of about 140,000 to about 250,000, and a surface energy of about 32mJ/m2 to about 38mJ/m 2. For convenience, the process according to this paragraph is sometimes referred to herein as terpolymer 7.
The present invention includes a terpolymer of Chlorotrifluoroethylene (CTFE), Vinyl Chloride (VC), and maleic acid consisting of chlorotrifluoroethylene monomer units, vinyl chloride monomer units, and maleic acid monomer units, the copolymer having a Tg of about 70 ℃ to about 87 ℃, a molecular weight of about 100,000 to about 300,000, and a surface energy of about 30mJ/m2 to about 40mJ/m 2. For convenience, the process according to this paragraph is sometimes referred to herein as terpolymer 8.
The present invention includes a terpolymer of Chlorotrifluoroethylene (CTFE), Vinyl Chloride (VC), and maleic acid consisting of chlorotrifluoroethylene monomer units, vinyl chloride monomer units, and maleic acid monomer units, the copolymer having a Tg of about 70 ℃ to about 87 ℃, a molecular weight of about 140,000 to about 250,000, and a surface energy of about 30mJ/m2 to about 40mJ/m 2. For convenience, the process according to this paragraph is sometimes referred to herein as a terpolymer 10.
The present invention includes a terpolymer of Chlorotrifluoroethylene (CTFE), Vinyl Chloride (VC), and maleic acid consisting of chlorotrifluoroethylene monomer units, vinyl chloride monomer units, and maleic acid monomer units, the terpolymer having a Tg of about 75 ℃ to about 87 ℃, a molecular weight of about 140,000 to about 250,000, and a surface energy of about 32mJ/m2 to about 38mJ/m 2. For convenience, the terpolymer according to this paragraph is sometimes referred to herein as terpolymer 10.
The present invention includes a terpolymer of Chlorotrifluoroethylene (CTFE), Vinyl Chloride (VC), and Maleic Acid (MA) consisting essentially of from about 5 wt% to about 50 wt% chlorotrifluoroethylene monomer units, from about 50 wt% to about 95 wt% vinyl chloride monomer units, and about 15 wt% or less maleic acid monomer units, the terpolymer having a Tg of from about 70 ℃ to about 87 ℃. For convenience, the terpolymer according to this paragraph is sometimes referred to herein as terpolymer 11.
The present invention includes a terpolymer of Chlorotrifluoroethylene (CTFE), Vinyl Chloride (VC), and Maleic Acid (MA) consisting essentially of from about 5 wt% to about 50 wt% chlorotrifluoroethylene monomer units, from about 50 wt% to about 95 wt% vinyl chloride monomer units, and about 15 wt% or less maleic acid monomer units, the terpolymer having a Tg of from about 75 ℃ to about 87 ℃. For convenience, the terpolymer according to this paragraph is sometimes referred to herein as terpolymer 12.
The present invention includes a terpolymer of Chlorotrifluoroethylene (CTFE), Vinyl Chloride (VC), and Maleic Acid (MA) that consists essentially of the terpolymer having a Tg of from about 70 ℃ to about 87 ℃, a molecular weight of from about 140,000 to about 250,000, and a surface energy of from about 32mJ/m2 to about 38mJ/m 2. For convenience, the terpolymer according to this paragraph is sometimes referred to herein as terpolymer 13.
The present invention includes a terpolymer of Chlorotrifluoroethylene (CTFE), Vinyl Chloride (VC), and Maleic Acid (MA) consisting essentially of from about 5 wt% to about 50 wt% chlorotrifluoroethylene monomer units, from about 50 wt% to about 95 wt% vinyl chloride monomer units, and about 15 wt% or less maleic acid monomer units, the terpolymer having a Tg of from about 75 ℃ to about 87 ℃, a molecular weight of from about 140,000 to about 250,000, and a surface energy of from about 32mJ/m2 to about 38mJ/m 2. For convenience, the terpolymer according to this paragraph is sometimes referred to herein as terpolymer 14.
The present invention includes a terpolymer of Chlorotrifluoroethylene (CTFE), Vinyl Chloride (VC), and Maleic Acid (MA) that consists of from about 5 wt% to about 50 wt% chlorotrifluoroethylene monomer units, from about 50 wt% to about 95 wt% vinyl chloride monomer units, and about 15 wt% or less maleic acid monomer units, the terpolymer having a Tg of from about 70 ℃ to about 87 ℃. For convenience, the terpolymer according to this paragraph is sometimes referred to herein as terpolymer 15.
The present invention includes a terpolymer of Vinyl Chloride (VC) and Maleic Acid (MA) consisting of about 5 wt% to about 50 wt% chlorotrifluoroethylene monomer units, about 50 wt% to about 95 wt% vinyl chloride monomer units, and about 15 wt% or less maleic acid monomer units, the terpolymer having a Tg of about 75 ℃ to about 87 ℃. For convenience, the terpolymer according to this paragraph is sometimes referred to herein as terpolymer 16.
The present invention includes a terpolymer of Chlorotrifluoroethylene (CTFE), Vinyl Chloride (VC), and Maleic Acid (MA) consisting of about 5 wt% to about 50 wt% chlorotrifluoroethylene monomer units, about 50 wt% to about 95 wt% maleic acid monomer units, and about 15 wt% or less maleic acid monomer units, the terpolymer having a Tg of about 70 ℃ to about 87 ℃, a molecular weight of about 140,000 to about 250,000, and a surface energy of about 32mJ/m2 to about 38mJ/m 2. For convenience, the terpolymer according to this paragraph is sometimes referred to herein as terpolymer 17.
The present invention includes a terpolymer of Chlorotrifluoroethylene (CTFE), Vinyl Chloride (VC), and Maleic Acid (MA) consisting of about 5 wt% to about 50 wt% chlorotrifluoroethylene monomer units, about 50 wt% to about 95 wt% vinyl chloride monomer units, and about 15 wt% or less maleic acid monomer units, the terpolymer having a Tg of about 75 ℃ to about 87 ℃, a molecular weight of about 140,000 to about 250,000, and a surface energy of about 32mJ/m2 to about 38mJ/m 2. For convenience, the terpolymer according to this paragraph is sometimes referred to herein as terpolymer 18.
In each of the above descriptions of terpolymers 1-18, the amount of maleic acid monomer units may be about 10% or less, and for convenience such terpolymers are referred to herein as terpolymers 1A-18A, respectively.
In each of the above descriptions of terpolymers 1-18, the maleic acid and maleic acid monomer units may be replaced by a third monomer that improves the hydrophilicity of the terpolymer but does not adversely affect other advantageous properties of the terpolymer as described herein. In each of the above descriptions of terpolymers 1-18, maleic acid and maleic acid monomer units may be replaced by a third monomer of such definition, and for convenience such terpolymers are referred to herein as terpolymers 1B-18B, respectively.
In each of the above descriptions of terpolymers 1-18, maleic acid may be replaced by a third monomer selected from the group consisting of methyl vinyl ether, ethyl vinyl ether, N-butyl vinyl ether, isobutyl vinyl ether, cyclohexyl vinyl ether, hydroxybutyl vinyl ether, 1, 4-cyclohexanedimethanol monovinyl ether, 3-aminopropyl vinyl ether, 1, 4-butanediol divinyl ether, diethylene glycol divinyl ether, 1, 4-cyclohexanedimethanol divinyl ether, vinyl acetate, vinyl propionate, vinyl benzoate, vinyl chloroformate, vinyl cinnamate, vinyl alcohol, N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylimidazole, N-vinyl-N-methylacetamide, acrylic acid, methacrylic acid, maleic, Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, benzyl acrylate, benzyl methacrylate, acrylamide, maleic acid, N-methylmaleimide, N-ethylmaleimide, methyl maleate, ethyl maleate, allylamine, and combinations of two or more thereof, and for convenience such terpolymers are referred to herein as terpolymers 1C-18C, respectively.
The present invention also includes films, fibers, films, coatings and other articles comprising inventive copolymers of the present invention, including any of copolymers 1-18.
The present invention also includes films, fibers, films, coatings and other articles comprising inventive copolymers of the present invention, including any of copolymers 1-18.
The present invention also includes films, fibers, membranes, coatings and other articles comprising the inventive terpolymers of the present invention, including any one of terpolymers 1-18.
The present invention also includes films, fibers, films, coatings, and other articles comprising the inventive terpolymers of the present invention, including any one of terpolymers 1A-18A.
The present invention also includes films, fibers, films, coatings and other articles comprising the inventive terpolymers of the present invention, including any one of terpolymers 1B-18B.
The invention also includes the use in films, fibers, films, coatings and other articles comprising the inventive terpolymers of the present invention, including any one of terpolymers 1C-18C.
The present invention also includes methods and processes of using the copolymers of the present invention, including any of copolymers 1-18, that can be advantageously improved by using articles prepared according to the present invention, including separation methods such as reverse osmosis desalination, microfiltration, ultrafiltration, nanofiltration, membrane distillation, pervaporation, and selective gas separation.
The present invention also includes methods and processes of using the terpolymers of the present invention (including any of terpolymers 1-18, terpolymers 1A-18A, terpolymers 1B-18B, and terpolymers 1C-18C) that can be advantageously improved by using articles prepared according to the present invention, including separation methods such as reverse osmosis desalination, microfiltration, ultrafiltration, nanofiltration, membrane distillation, pervaporation, and selective gas separation.
The present invention also provides the inventive process for synthesizing a copolymer comprising chlorotrifluoroethylene monomer units and vinyl chloride monomer units and/or a terpolymer comprising chlorotrifluoroethylene monomer units, vinyl chloride monomer units and maleic acid units. The method comprises the following steps: (a) providing an initial reaction medium comprising chlorotrifluoroethylene monomer and vinyl chloride monomer, CTFE: a VC weight ratio of about 50:50 to about 5: 95; and (b) reacting the chlorotrifluoroethylene monomer and vinyl chloride monomer under conditions to produce a copolymer or terpolymer comprising vinyl chloride monomer units, the weight percentage of vinyl chloride monomer units (based on the total weight of the produced copolymer or terpolymer) being within 20% of the weight percentage of VC monomer in the initial reaction medium. For convenience, the method according to this paragraph is sometimes referred to herein as method 1.
The method of the invention also comprises the following steps: (a) providing an initial aqueous reaction medium comprising at least one free radical initiator and chlorotrifluoroethylene monomer and vinyl chloride monomer in a CTFE to VC weight ratio of about 50:50 to about 5: 95; and (b) reacting the chlorotrifluoroethylene monomer and vinyl chloride monomer under conditions to produce a copolymer or terpolymer comprising vinyl chloride monomer units, the weight percentage of vinyl chloride monomer units (based on the total weight of the produced copolymer or terpolymer) being within 15% of the weight percentage of VC monomer in the initial reaction medium, wherein the conditions comprise conducting the reaction at a temperature in the range of about 20C to about 50C for a period of at least about 15 hours. For convenience, the method according to this paragraph is sometimes referred to herein as method 2.
The method of the invention also comprises the following steps: (a) providing an initial aqueous reaction medium comprising at least one free radical initiator and chlorotrifluoroethylene monomer and vinyl chloride monomer in a CTFE to VC weight ratio of about 50:50 to about 5: 95; and (b) reacting the chlorotrifluoroethylene monomer and vinyl chloride monomer under conditions to produce a copolymer or terpolymer comprising vinyl chloride monomer units, the weight percentage of vinyl chloride monomer units (based on the total weight of the produced copolymer or terpolymer) being within 10% of the weight percentage of VC monomer in the initial reaction medium, wherein the conditions comprise conducting the reaction at a temperature in the range of about 20C to about 50C for a period of at least about 15 hours to produce a copolymer having a glass transition temperature of about 70 ℃ to about 87 ℃. For convenience, the method according to this paragraph is sometimes referred to herein as method 3.
The method of the invention also comprises the following steps: (a) providing an aqueous reaction medium comprising at least one free radical initiator and chlorotrifluoroethylene monomer and vinyl chloride monomer in a CTFE to VC weight ratio of about 50:50 to about 5:95 based on total CTFE and VC monomers introduced into the reaction medium; and (b) reacting said chlorotrifluoroethylene monomer and vinyl chloride monomer under conditions to produce a copolymer or terpolymer comprising vinyl chloride monomer units, the weight percent of said vinyl chloride monomer units being within 5% of the weight percent of said VC monomer introduced to said reaction medium (based on the total monomers introduced to said reaction medium). For convenience, the method according to this paragraph is sometimes referred to herein as method 4.
The method of the invention also comprises the following steps: (a) providing an aqueous reaction medium comprising at least one free radical initiator and chlorotrifluoroethylene monomer and vinyl chloride monomer in a CTFE to VC weight ratio of about 50:50 to about 5:95 based on total CTFE and VC monomers introduced into the reaction medium; and (b) reacting the chlorotrifluoroethylene monomer and vinyl chloride monomer under conditions to produce a copolymer or terpolymer comprising vinyl chloride monomer units, the weight percent of the vinyl chloride monomer units being within 5% of the weight percent of the VC monomer introduced into the reaction medium (based on the total monomers introduced into the reaction medium), wherein the conditions comprise conducting the reaction at a temperature in the range of about 20C to about 50C for a period of at least about 15 hours to produce a copolymer having a glass transition temperature of about 70 ℃ to about 87 ℃. For convenience, the method according to this paragraph is sometimes referred to herein as method 5.
The method of the invention also comprises the following steps: (a) providing an aqueous reaction medium comprising at least one free radical initiator and chlorotrifluoroethylene monomer and vinyl chloride monomer in a CTFE to VC weight ratio of about 50:50 to about 5:95 based on total CTFE and VC monomers introduced into the reaction medium; and (b) reacting said chlorotrifluoroethylene monomer and vinyl chloride monomer under conditions to produce a copolymer or terpolymer comprising vinyl chloride monomer units, the weight percent of said vinyl chloride monomer units being within 2% of the weight percent of said VC monomer introduced to said reaction medium (based on the total monomers introduced to said reaction medium). For convenience, the method according to this paragraph is sometimes referred to herein as method 6.
The method of the invention also comprises the following steps: (a) providing an aqueous reaction medium comprising at least one free radical initiator and chlorotrifluoroethylene monomer and vinyl chloride monomer in a CTFE to VC weight ratio of about 50:50 to about 5:95 based on total CTFE and VC monomers introduced into the reaction medium; and (b) reacting the chlorotrifluoroethylene monomer and vinyl chloride monomer under conditions to produce a copolymer or terpolymer comprising vinyl chloride monomer units, the weight percent of the vinyl chloride monomer units being within 2% of the weight percent of the VC monomer introduced to the reaction medium (based on the total monomers introduced to the reaction medium), wherein the conditions comprise conducting the reaction at a temperature in the range of about 20C to about 50C for a period of at least about 15 hours to produce a copolymer having a glass transition temperature of about 70 ℃ to about 87 ℃. For convenience, the method according to this paragraph is sometimes referred to herein as method 7.
The method of the invention also comprises the following steps: (a) providing an aqueous reaction medium comprising at least one free radical initiator and chlorotrifluoroethylene monomer and vinyl chloride monomer in a CTFE to VC weight ratio of about 50:50 to about 5:95 based on total CTFE and VC monomers introduced into the reaction medium; and (b) reacting said chlorotrifluoroethylene monomer and vinyl chloride monomer under conditions to produce a copolymer or terpolymer comprising vinyl chloride monomer units, the weight percent of said vinyl chloride monomer units being within 1% of the weight percent of said VC monomer introduced to said reaction medium (based on the total monomers introduced to said reaction medium). For convenience, the method according to this paragraph is sometimes referred to herein as method 8.
The method of the invention also comprises the following steps: (a) providing an aqueous reaction medium comprising at least one free radical initiator and chlorotrifluoroethylene monomer and vinyl chloride monomer in a CTFE to VC weight ratio of about 50:50 to about 5:95 based on total CTFE and VC monomers introduced into the reaction medium; and (b) reacting the chlorotrifluoroethylene monomer and vinyl chloride monomer under conditions to produce a copolymer or terpolymer comprising vinyl chloride monomer units, the weight percent of the vinyl chloride monomer units being within 1% of the weight percent of the VC monomer introduced into the reaction medium (based on the total monomers introduced into the reaction medium), wherein the conditions comprise conducting the reaction at a temperature in the range of about 20C to about 50C for a period of at least about 15 hours to produce a copolymer having a glass transition temperature of about 70 ℃ to about 87 ℃. For convenience, the method according to this paragraph is sometimes referred to herein as method 9.
The present invention includes copolymers, including any of copolymers 1-18, prepared according to the methods of the present invention, including any of methods 1-9.
The present invention includes terpolymers, including any of terpolymers 1-18, terpolymers 1A-18A, terpolymers 1B-18B, and terpolymers 1C-18C, produced according to the process of the present invention, including any of processes 1-9.
The present invention includes terpolymers, including any one of terpolymers 1-18 and terpolymers 1A-18A, made according to any one of processes 1-9, wherein the step of providing an aqueous reaction medium includes providing an aqueous reaction medium further comprising at least maleic acid or maleic anhydride, and wherein the step of reacting includes reacting the chlorotrifluoroethylene monomer and the vinyl chloride monomer and the maleic acid or anhydride.
The present invention includes terpolymers, including any of terpolymers 1-18, terpolymers 1B-18B and terpolymers 1C-18C, produced according to any of methods 1-9, wherein the step of providing an aqueous reaction medium includes providing an aqueous reaction medium further comprising at least one of the third monomers, and wherein the step of reacting includes reacting the chlorotrifluoroethylene monomer with the vinyl chloride monomer and at least one of the third monomers.
Detailed Description
The copolymers and terpolymers according to the invention are formed by a polymerization reaction comprising reacting chlorotrifluoroethylene monomer and vinyl chloride monomer in a reaction medium. The present invention provides copolymers of chlorotrifluoroethylene and vinyl chloride and terpolymers of CTFE, VC and MA.
In a preferred embodiment, chlorotrifluoroethylene monomer and vinyl chloride monomer, and maleic acid monomer or third polymer (when present), are polymerized in an aqueous solution using a water-soluble initiator or a water-soluble redox initiator system to obtain a CTFE/VC copolymer or CTFE/VC/MA terpolymer or CTFE/VC/third monomer terpolymer having a high glass transition temperature. The aqueous solution may be free of suspending or emulsifying agents.
The present invention provides a copolymer comprising chlorotrifluoroethylene monomer units and vinyl chloride monomer units. In certain embodiments of the invention, the copolymer comprises from about 5% to about 50% by weight chlorotrifluoroethylene monomer units and from about 50% to about 95% by weight vinyl chloride monomer units. The copolymers and terpolymers preferably have a weight average molecular weight of about 10,000 to about 500,000. The copolymers and terpolymers preferably have a glass transition temperature of about 70 ℃ to about 87 ℃. The copolymers and terpolymers preferably have a thickness of between about 30mJ/m2And about 40mJ/m2Surface energy in between.
The present invention provides methods for preparing membranes of chlorotrifluoroethylene and vinyl chloride copolymers, and membranes of CTFE/VC/MA terpolymers and CTFE/VC/third monomer terpolymers. In certain embodiments of the invention, the CTFE/VC and CFTE/VC/MA and CTFE/VC/third monomer polymer films are prepared by non-solvent induced phase separation (NIPS) and Thermally Induced Phase Separation (TIPS) methods. In the case of porous membrane preparation, it is preferred to use one or more pore formers to control the density and size of the pores formed.
The present invention provides films prepared from CTFE/VC copolymers and films prepared from CTFE/VC/MA and films of CTFE/VC/third monomer terpolymers. In certain embodiments of the invention, the CTFE/VC and CTFE/VC/MA and CTFE/VC/third monomer polymer membranes are non-porous. In other embodiments of the invention, the CTFE/VC and CTFE/VC/MA and CTFE/VC/third monomer polymer membranes are porous. The CTFE/VC, the CTFE/VC/MA and the CTFE/VC/third monomer polymer film can be an asymmetric integral involucra film or a thin film composite film. The CTFE/VC and CTFE/VC/MA and CTFE/VC/third monomer polymer films may have a flat sheet configuration or a hollow fiber configuration.
In certain embodiments of the invention, the CTFE/VC polymer membranes and the CTFE/VC/MA polymer membranes and the CTFE/VC/third monomer polymer membranes are used as reverse osmosis membranes, filtration membranes, distillation membranes, pervaporation membranes and selective gas separation membranes. In other embodiments of the invention, CTFE/VC and CTFE/VC/MA and CTFE/VC/third monomer polymer membranes are used in batteries such as lithium ion batteries and fuel cells.
The invention also provides a coating prepared from the CTFE/VC copolymer, the CTFE/VC/MA and the CTFE/VC/third monomer terpolymer. In certain embodiments of the invention, the CTFE/VC and CTFE/VC/MA and CTFE/VC/third monomer polymer coating have a thickness of about 30mJ/m2To about 40mJ/m2The surface energy of (1). The CTFE/VC and CTFE/VC/MA third monomer polymer coatings are coil coatings, anti-reflection coatings, biological-resistant coatings, flame-retardant coatings, coatings of plastic optical fibers and protective coatings. The CTFE/VC and CTFE/VC/MA and CTFE/VC/third monomer polymer coatings on the article are formed, for example, by dip coating, spray coating, or coil coating.
The present invention also provides barrier materials for CTFE/VC copolymers and CTFE/VC/MA terpolymers to provide moisture and oxygen resistance. The present invention provides membranes made from CTFE/VC copolymers and CTFE/VC/MA and CTFE/VC/third monomer terpolymers. In certain embodiments of the invention, the CTFE/VC and CTFE/VC/MA and CTFE/VC/third monomer polymer films have a thickness of about 30mJ/m2To about 40mJ/m2The surface energy of (1). CTFE/VC and CTFE/VC/MA and CTFE/VC/third monomer polymer films are formed by, for example, solution casting or extrusion. CTFE/VC and CTFE/VC/MA and CTFE/VC/third monomer polymer films are useful in packaging to provide moisture and oxygen resistance.
The invention provides fibers made from CTFE/VC copolymers and CTFE/VC/MA and CTFE/VC/third monomer terpolymers. In certain embodiments of the invention, the VC/CTFE and CTFE/VC/MA polymer fibers are formed by extrusion.
In certain embodiments of the present invention, CTFE/VC copolymers and CTFE/VC/MA and CTFE/VC/third monomer terpolymers are used as binders. In other embodiments of the invention, the CTFE/VC copolymer and CTFE/VC/MA and CTFE/VC/third monomer terpolymer are used as electrode binders for batteries such as lithium ion batteries.
CTFE/VC/MA and CTFE/VC/third monomer terpolymers have improved properties, and in particular solubility, hydrophilicity, adhesion and crosslinking, for use in films, coatings, extruded articles and other applications. Membranes made from the CTFE/VC/MA and CTFE/VC/third monomer terpolymers according to the invention are useful for separation applications including reverse osmosis desalination, nanofiltration, ultrafiltration, microfiltration, membrane distillation, pervaporation and selective gas separation.
The present invention provides copolymers of Chlorotrifluoroethylene (CTFE) and Vinyl Chloride (VC) and terpolymers of CTFE, VC, and MA and terpolymers of CTFE, VC, and a third monomer as described herein having improved properties, and in particular high glass transition temperatures, for use in films, and coatings. The membranes according to the invention are used in separation applications including reverse osmosis desalination, nanofiltration, ultrafiltration, microfiltration, membrane distillation, pervaporation and selective gas separation. The membranes according to the invention are also used in batteries such as lithium ion batteries and fuel cells. The coating may be a coil coating, an anti-reflective coating, a bio-resistant coating, a flame retardant coating, a coating for plastic optical fiber, and a protective coating. In other embodiments, the copolymer is used in barrier films to provide moisture and oxygen resistance.
Copolymer and terpolymer compositions
The present invention provides copolymers and terpolymers comprising chlorotrifluoroethylene monomer units and vinyl chloride monomer units. The copolymers and terpolymers preferably comprise about 5 wt% to about 50 wt% CTFE monomer units and about 50 wt% to about 95 wt% VC monomer units.
Vinyl chloride monomer units may be present in the preferred copolymers and preferred terpolymers in an amount of at least about 50 wt%, at least about 60 wt%, at least about 65 wt%, at least about 70 wt%, at least about 75 wt%, or at least about 80 wt%, and up to about 85 wt%, or up to about 90 wt%, or up to about 95 wt% of the monomers in the copolymer or terpolymer.
The CTFE monomer units may be present in an amount of at least about 5 wt%, or at least about 10 wt%, at least about 15 wt%, and up to about 50 wt%, up to about 40 wt%, or up to about 35 wt%, or up to about 30 wt% of the monomers in the copolymer or terpolymer.
The vinyl chloride monomer may comprise from about 50% to about 95% by weight of the monomers of the copolymer or terpolymer, or from about 60% to about 90% by weight of the monomers of the copolymer or terpolymer, or from about 65% to about 95% by weight of the monomers of the copolymer or terpolymer, or from about 65% to about 90% by weight of the monomers of the copolymer or terpolymer, or from about 70% to about 95% by weight of the monomers of the copolymer or terpolymer, or from about 70% to about 90% by weight of the monomers of the copolymer or terpolymer, or from about 75% to about 95% by weight of the monomers of the copolymer or terpolymer, or from about 75% to about 90% by weight of the monomers of the copolymer or terpolymer, or from about 80% to about 90% by weight of the monomers of the copolymer or terpolymer, Or from about 80 to about 95 weight percent of the monomers of the copolymer or terpolymer.
Accordingly, the CTFE monomer may comprise from about 5% to about 50% by weight of the monomers of the copolymer or terpolymer, or from about 5% to about 40% by weight of the monomers of the copolymer or terpolymer, or from about 10% to about 40% by weight of the monomers of the copolymer or terpolymer, or from about 5% to about 35% by weight of the monomers of the copolymer or terpolymer, or from about 10% to about 35% by weight of the monomers of the copolymer or terpolymer, or from about 5% to about 30% by weight of the monomers of the copolymer or terpolymer, or from about 10% to about 30% by weight of the monomers of the copolymer or terpolymer, or from about 5% to about 25% by weight of the monomers of the copolymer or terpolymer, or from about 10% to about 20% by weight of the monomers of the copolymer or terpolymer, Or from about 5 to about 20 weight percent of the monomers of the copolymer or terpolymer.
In another embodiment, the vinyl chloride monomer may comprise from about 50% to about 75% by weight of the monomers of the copolymer or terpolymer, or from about 55% to about 75% by weight of the monomers of the copolymer or terpolymer, or from about 60% to about 75% by weight of the monomers of the copolymer or terpolymer, or from about 65% to about 75% by weight of the monomers of the copolymer or terpolymer, or from about 50% to about 70% by weight of the monomers of the copolymer or terpolymer, or from about 55% to about 65% by weight of the monomers of the copolymer or terpolymer. Accordingly, the CTFE monomer may comprise from about 25% to about 50% by weight of the monomers of the copolymer or terpolymer, or from about 25% to about 45% by weight of the monomers of the copolymer or terpolymer, or from about 25% to about 40% by weight of the monomers of the copolymer or terpolymer, or from about 25% to about 35% by weight of the monomers of the copolymer or terpolymer, or from about 30% to about 50% by weight of the monomers of the copolymer or terpolymer, or from about 30% to about 45% by weight of the monomers of the copolymer or terpolymer, or from about 35% to about 45% by weight of the monomers of the copolymer or terpolymer.
The copolymer or terpolymer used in the present invention may comprise vinyl chloride and CTFE monomers in the weight percentages described above. The copolymer or terpolymer used in the present invention may consist essentially of the above-described weight percentages of vinyl chloride and CTFE monomers. The fluorocopolymer to be used in the present invention may consist of the above-mentioned weight percentages of vinyl chloride and CTFE monomers.
The ratio of chlorotrifluoroethylene monomer units to vinyl chloride monomer units in the copolymer or terpolymer of the invention is from about 50:50 weight percent to about 5:95 weight percent by weight.
Process for preparing copolymers or terpolymers
The copolymer or terpolymer according to the present invention is formed by copolymerization or terpolymerization of monomers comprising CTFE and VC. The present invention provides a method of synthesizing a copolymer or terpolymer comprising chlorotrifluoroethylene monomer units and vinyl chloride monomer units. The amount of monomers charged in the process is about 5 wt% to about 50 wt% CTFE and correspondingly about 50 wt% to about 95 wt% VC. In a preferred embodiment, chlorotrifluoroethylene monomer and vinyl chloride monomer are charged in one shot. Polymerizing chlorotrifluoroethylene monomer and vinyl chloride monomer in an aqueous solution using a water-soluble initiator or a water-soluble redox initiator system to obtain a CTFE/VC copolymer or a CTFE/VC/MA or a CTFE/VC/third monomer terpolymer having a high glass transition temperature. The aqueous solution is preferably free of suspending or emulsifying agents.
The copolymerization or terpolymerization of chlorotrifluoroethylene and vinyl chloride monomer (and MA or a third monomer, when present) may be carried out in aqueous solution, in particular in aqueous solution that may be used in connection with free radical polymerization. The water-soluble free radical initiator may include any compound that initiates copolymerization of chlorotrifluoroethylene and vinyl chloride monomer. Non-limiting examples of such initiators include Na2S2O8、K2S2O8、(NH4)2S2O8、Fe2(S2O8)3、(NH4)2S2O8/Na2S2O5、(NH4)2S2O8/FeSO4、(NH4)2S2O8/Na2S2O5/FeSO4T-butyl hydroperoxide, and the like, and combinations thereof.
The polymerization is generally conducted at a temperature, pressure, and length of time sufficient to produce the desired chlorotrifluoroethylene/vinyl chloride copolymer or CTFE/VC/MO or CTFE/VC/third monomer terpolymer, and may be conducted in any reactor known for such purposes, such as, but not limited to, an autoclave reactor.
In one embodiment of the invention, the polymerization is conducted at a temperature of from about 10 ℃ to about 80 ℃ and a pressure of from about 10psi to about 300 psi. The length of polymerization can be any length of time to achieve the desired degree of polymerization. In certain non-limiting embodiments, it can be between about 10 hours and about 100 hours. Those skilled in the art will appreciate that such conditions may be improved or varied based on the desired conversion and molecular weight of the resulting chlorotrifluoroethylene/vinyl chloride copolymer or CTFE/VC/MO or CTFE/VC/third monomer terpolymer.
The amount of initiator may be provided to control the conversion of the copolymer or terpolymer produced and/or the molecular weight of the copolymer produced. Generally, although not exclusively, the free radical initiator is provided at a concentration of less than 2.0 weight percent based on the weight of all monomers in the copolymerization or terpolymerization reaction.
The initiator may be added to the copolymerization or terpolymerization system multiple times or in a continuous mode to obtain the desired copolymer or terpolymer yield and molecular weight of the copolymer or terpolymer produced. Generally, although not exclusively, the initiator is added to the polymerization system from 1 to 3 times.
In a preferred embodiment of the invention, the copolymerization of chlorotrifluoroethylene and vinyl chloride monomer or the terpolymerization of chlorotrifluoroethylene and vinyl chloride monomer with MA or a third monomer is carried out in an aqueous solution of degassed deionized water, including (NH)4)2S2O8And Na2S2O5Redox initiator of (2) and catalyst FeSO4And (4) forming.
Copolymer and terpolymer Properties
The ratio of monomer units of the copolymer or terpolymer is determined by elemental analysis of the copolymer.
The present invention provides copolymers and terpolymers as described herein, wherein the copolymer or terpolymer has a weight average molecular weight of about 10,000 daltons to about 500,000 daltons. The copolymer or terpolymer may have a weight average molecular weight greater than about 20,000 daltons, or greater than about 30,000 daltons, or greater than about 50,000 daltons, or greater than about 100,000 daltons. The copolymer or terpolymer as described herein can have a weight average molecular weight of less than 500,000 daltons, less than about 300,000 daltons, or less than 250,000 daltons, or less than 200,000 daltons.
Weight average molecular weight as used herein was measured by gel permeation chromatography using Agilent Technologies PL-GPC-20 high temperature chromatograph equipped with two columns: 300X 7.5mm PL-GEL 5 μmix B support column and a second 300X 7.5mm PL-GEL 5 μmix C support column. The eluent for this system was THF. The system was equilibrated at 40C. Standardization is provided by using polystyrene, PS-M polystyrene standards. The method is described in MODERN SIZE EXCLUSION LIQUID CHROMATOGRAPHY Practice of Gel Permeation and Gel filtration CHROMATOGRAPHY, SECOND EDITION, Andre m.striegel, Wallace w.yau, Joseph j.kirkland Donald d.bly,2009, John wilkinson publishers (model SIZE-EXCLUSION resource library Practice of Gel Permeation and Donald d.ble., Wallace w.yau, Joseph kirilog and Donald b.ble., 2009, John company).
The copolymers and terpolymers of the present invention have a glass transition temperature of from about 70 ℃ to about 87 ℃, or from about 75 ℃ to about 85 ℃. The glass transition temperature was measured by a DSC Q200 apparatus (TA) at a temperature rise of 10 ℃/min (see B.Wanderlich, "thermal analysis", Academic Press,1990, p.417-431 (B.Wanderlich, thermal analysis, Academic Press,1990, pp. 417-431)).
The copolymers and terpolymers of the present invention have a thickness of between about 30mJ/m2And about 40mJ/m2Surface energy in between. The surface energy of the copolymer is determined by water and diiodomethane contact angle measurements on the smooth surface of the copolymer coated on a glass slide, methods well known in the art.
Copolymer treatment
The chlorotrifluoroethylene/vinyl chloride copolymers of the present invention as well as CTFE/VC/Ma and CTFE/VC/third monomer terpolymers may also be soluble in certain organic solvents at elevated temperatures. Such hot solutions can be used as casting or spinning solutions for film forming. Examples of such solvents include, but are not limited to, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, and the like.
The film, film or coating composition may optionally comprise one or more additives. Non-limiting examples of such additives are organic compounds, polymers, inorganic compounds, metals, metal oxides, and the like, or combinations thereof. Additional or specific additives are provided herein or will be apparent to the skilled artisan based on the disclosure herein.
The chlorotrifluoroethylene/vinyl chloride and CTFE/VC/Ma and CTFE/VC/third monomer polymer membranes of the present invention can be processed into shapes in both flat sheet configurations and hollow fiber configurations. The flat membrane and the hollow fiber membrane may be asymmetric integral membranes produced from a casting solution or a spinning solution by a phase separation method. Asymmetric integrally skinned flat sheet membranes and hollow fiber membranes have a thin, dense, non-porous or porous selective skin layer that performs the separation and is supported on a highly porous substrate layer made of the same material.
Flat sheet membranes and hollow fiber membranes can also be Thin Film Composite (TFC) membranes prepared by lamination or dip coating techniques. TFC membranes include a thin, dense, non-porous or porous selective layer that performs separation and a highly porous substrate layer made separately of different materials.
The hollow fiber membranes preferably have a high membrane area and are self-supporting membranes.
The chlorotrifluoroethylene/vinyl chloride copolymer and CTFE/VC/Ma and CTFE/VC/third monomer polymer films may be prepared by a non-solvent induced phase separation (NIPS) method. In the case of porous membrane preparation, one or more pore-forming agents are used to control the density and size of the pores formed in the porous CTFE/VC or CTFE/VC/MA or CTFE/VC/third monomer polymer membrane. Non-limiting examples of pore formers are glycerol, polyethylene glycol (PEG), and polyvinylpyrrolidone (PVP).
The membranes disclosed herein can have a uniform pore structure. Such films may be formed according to the Loeb-Sourirajan method.
The film may be formed by phase inversion. Polymer membranes (e.g. for water treatment) can be formed by phase inversion, and the resulting membranes are classified according to their pore size. Reverse osmosis membranes for water desalination typically comprise a diameter of about
Apparatuses for continuous process shaping of polymer films by phase inversion are known. Generally, the step involves dissolving the polymer in a solvent to form a solution comprising from about 10% to about 30% by weight of the polymer. Sometimes, a small amount of non-solvent and an organic or inorganic salt are added to the solution. The solution can be cast under a doctor blade onto a moving strip of non-woven polyester or Mylar (Mylar) film, which can be used as a permanent support for the finished film. The thickness of the blade gap and the viscosity of the polymer blend solution control the thickness of the film formed. The thickness of the film formed depends on the end use of the material and can vary from about 1 μm to 2 mm. Preferably, the formed film has a thickness of 10 μm to 500 μm, and most preferably 20 μm to 250 μm. The film is then immersed in a non-solvent (typically water), i.e. a fluid in which the polymer is substantially insoluble. This results in gelling of the polymer to form an asymmetric porous structure. The membrane may be heat treated in a second water bath to promote pore shrinkage.
The chlorotrifluoroethylene and vinyl chloride polymer membranes and CTFE/VC/MA and CTFE/MA/third monomer terpolymer membranes of the present invention have utility and/or exhibit advantages in separation applications where conventionally used polymer membranes have been employed. In certain highly preferred embodiments, membranes comprising chlorotrifluoroethylene and vinyl chloride copolymers, as well as the CTFE/VC/MA and CTFE/MA/third monomer terpolymer membranes of the present invention, are useful for reverse osmosis desalination, nanofiltration, ultrafiltration, microfiltration, membrane distillation, pervaporation, and selective gas separation.
(1) Reverse Osmosis (RO)
The CTFE/VC polymer film material, the CTFE/VC/MA and the CTFE/MA/third monomer terpolymer film material have the thickness of about 30mJ/m2And about 40mJ/m2Surface energy suitable for water treatment and purification. Furthermore, the CTFE/VC polymeric material and CTFE/VC/MA and CTFE/MA/third monomer terpolymer membrane material are stable over a wide pH range, which is desirable for RO separation. In addition, the CTFE/VC polymeric material and the CTFE/VC/MA and CTFE/MA/third monomer terpolymer film material are also resistant to microbial attack and oxychlorination.
Optionally, the CTFE/VC polymer membrane material and the CTFE/VC/MA and CTFE/MA/third monomer terpolymer membrane material may have increased hydrophilicity to increase water absorption and RO permeation flux.
(2) Microfiltration (MF), Ultrafiltration (UF) and Nanofiltration (NF)
In the last fifteen years PVDF has become popular for Microfiltration (MF) and Ultrafiltration (UF). However, compared to PVDF, the CTFE/VC polymer membrane materials and CTFE/VC/MA and CTFE/MA/third monomer terpolymer membrane materials of the present invention have more desirable surface energies for water filtration and are more resistant to corrosion and oxidation attack. The process forming parameters can be varied to obtain CTFE/VC polymer membranes and CTFE/VC/MA and CTFE/MA/third monomer terpolymer membrane materials with different structures, which are suitable for microfiltration, ultrafiltration and nanofiltration.
(3) Membrane Distillation (MD)
Membrane Distillation (MD) requires high hydrophobicity of the membrane material. Commercially available PTFE is generally an option; however, the solubility of PTFE is a problem with film forming. The CTFE/VC polymer material, the CTFE/VC/MA material and the CTFE/MA/third monomer terpolymer film material have adjustable surface energy according to monomer ratio. Furthermore, CTFE/VC polymeric materials and CTFE/VC/MA and CTFE/MA/third monomer terpolymer film materials are soluble in certain organic solvents, which present advantages over PTFE for film processing formation.
(4) Pervaporation (PV)
Pervaporation is a membrane process in which the permeating substance alters itThe phases of these. For example, polydimethylsiloxane and polyoctylmethylsiloxane are rubbery membrane materials and are permeable (i.e., organophilic) to organic substances. Pervaporation of polydimethylsiloxane or polyoctylmethylsiloxane membranes is used for separation of organic matter from water, such as in the food industry for flavor recovery and in wastewater treatment. In contrast, CTFE/VC copolymers and CTFE/VC/MA and CTFE/MA/third monomer terpolymers are of T as described hereingGlassy polymeric materials of value (e.g., about 80 ℃) are expected to open up new areas of organic separation.
(5) Selective gas separation
One important application of fluoropolymers is in the field of selective gas separation. Commercial examples in this area include TEFLON AF 2400 and AF 1600, HYFLON AD 80 and AD 60, and CYTOP. See "research in Industrial and engineering chemistry", 2009, volume 48, pages 4638-4663 (Ind. Eng. chem. Res.2009,48, 4638-4663). In CO2/CH4Upon separation, these fluoropolymers exhibit high CO2Permeability, but relatively low CO2/CH4And (4) selectivity. The nonporous asymmetric integral involucra membrane and the nonporous Thin Film Composite (TFC) membrane prepared by the CTFE/VC copolymer, the CTFE/VC/MA and the CTFE/MA/third polymer membrane terpolymer further improve the performance of selective gas separation.
The chlorotrifluoroethylene and vinyl chloride polymer film and CTFE/VC/MA and CTFE/MA/third monomer polymer film of the present invention also have utility and/or exhibit advantages in power supply devices and power stations to which conventionally used polymer films have been applied. In certain highly preferred embodiments, membranes comprising chlorotrifluoroethylene and vinyl chloride copolymers of the present invention and CTFE/VC/MA and CTFE/MA/third monomer are useful in batteries, such as lithium ion batteries and fuel cells.
The chlorotrifluoroethylene and vinyl chloride copolymers of the present invention, as well as CTFE/VC/MA and CTFE/MA/third monomer, may be applied to the support or article in any of a variety of ways commonly known in the art for forming coatings. CTFE/VC, CTFE/VC/MA and CTFE/MA/third monomer polymer coating toolHas a thickness of about 30mJ/m2To about 40mJ/m2The surface energy of (1). CTFE/VC and CTFE/VC/MA and CTFE/MA/third monomer polymer coatings are useful as corrosion resistant coatings, anti-reflective coatings, bio-resistant coatings, flame retardant coatings, coatings for plastic optical fibers, and protective coatings. The CTFE/VC and CTFE/VC/MA and CTFE/MA/third monomer polymer coatings on the article may be formed by dip coating, spray coating or coil coating. In a non-limiting example, the copolymer is dissolved as described in the examples below, and the copolymer solution is applied to a carrier or article and then dried.
The chlorotrifluoroethylene and vinyl chloride copolymers of the present invention are useful as barrier materials to achieve moisture and oxygen resistance. The CTFE/VC, the CTFE/VC/MA and the CTFE/MA/third monomer polymeric material can be used for food and drug packaging.
The chlorotrifluoroethylene and vinyl chloride copolymers of the present invention may be made into films. The CTFE/VC and CTFE/VC/MA and CTFE/MA/third monomer Polymer films have a thickness of about 30mJ/m2To about 40mJ/m2The surface energy of (1). CTFE/VC and CTFE/VC/MA and CTFE/MA/third monomer polymer films can be prepared by solution casting or extrusion.
The chlorotrifluoroethylene and vinyl chloride copolymers and CTFE/VC/MA and CTFE/MA/third monomer terpolymers of the present invention may be formed into fibers. CTFE/VC and CTFE/VC/MA and CTFE/MA/third monomer polymer fibers may be formed by extrusion.
Films and membranes comprising copolymers and terpolymers as described herein can have high surface energy and are resistant to fouling. The increase in hydrophilicity provides better fouling resistance because proteins and many other soils are hydrophobic in nature. Fouling resistance can be assessed by measuring the change in flux or flux through the membrane over time as the membrane is exposed to an agent that simulates fouling of the membrane during use. The test foulant was a solution of alginic acid, bovine serum albumin and humic acid. The solution tested for fouling agent was run through the membrane in a cross-flow apparatus. Flux reaches zero at fouling. Methods for fouling assays are described in Hyok Choi et al, "Influence of cross-flow velocity during filtration of biological suspensions" on Membrane performance, "Journal of Membrane Science, Vol.248, stages 1-2, 15.2.2005, pp.189-. When tested according to this method, the membranes of the invention showed longer fouling times compared to conventional membranes.
Films comprising copolymers and terpolymers as described herein have excellent chemical stability. Chemical stability is particularly important to allow the membrane to withstand the conditions typically used to clean the membrane. Thus, the membrane has high alkali resistance and is stable when treated with a solution having a pH of 9 or higher and preferably has a pH up to pH 13. Preferably, the copolymer film exhibits a weight change of about 1% or less when exposed to a 5% NaOH solution at 50 ℃ for 30 days.
The copolymer and terpolymer films also preferably have high resistance to oxidizing agents (e.g., bleach) typically used for cleaning. Preferably, the copolymer and terpolymer films exhibit a weight loss of about 1.5% or less when exposed to a 5% NaClO solution (bleaching solution) at 50 ℃ for 30 days.
The copolymer and terpolymer films also preferably have high resistance to acids commonly used for cleaning. Preferably, the copolymer and terpolymer films exhibit a weight change of about 0.5% or less when exposed to 5% citric acid at 50 ℃ for 30 days.
In addition, the film has a high tolerance for cleaning temperatures greater than about 40 ℃, and preferably up to about 50 ℃ or more.
Copolymer and terpolymer films and films preferably exhibit high flexibility to help prevent cracking. The modulus of elasticity is a measure of the ability to elastically (i.e., non-permanently) deform in response to an applied force. The elastic modulus is the slope of its stress-strain curve in the elastically deformed region. The elastic modulus of the copolymer and terpolymer films and films as described herein is preferably between about 600MPa and 2400 MPa; and more preferably in the range of about 1500 to 2400MPa as measured according to ASTM D638.
Comprising the copolymer described hereinAnd a terpolymer, as measured by ASTM D3985 using MOCON ox-Tran 2/20. Thus, the film has less than about 0.01 g/(m)2Days), and preferably less than about 0.005 g/(m)2Day) oxygen permeability.
Films comprising copolymers as described herein have low moisture permeability as measured by ASTM F1249 using mocomperma-Tran 3/31. Thus, the film has less than about 0.01 g/(m)2Days), and preferably less than about 0.005 g/(m)2Day) moisture permeability.
The chlorotrifluoroethylene and vinyl chloride copolymers and CTFE/VC/MA and CTFE/MA/third monomer terpolymers of the present invention are useful as binders. Thus, the CTFE/VC polymer and CTFE/VC/MA and CTFE/MA/third monomer terpolymer are useful as electrode binders for lithium ion batteries. The capacity retention of the lithium ion battery is higher than 85% after 50 discharge and recharge cycles. The coulomb efficiency of the lithium ion battery is higher than 99%.
The present invention also provides terpolymers of Chlorotrifluoroethylene (CTFE), Vinyl Chloride (VC), and a third monomer. The third monomer may be methyl vinyl ether, ethyl vinyl ether, N-butyl vinyl ether, isobutyl vinyl ether, cyclohexyl vinyl ether, hydroxybutyl vinyl ether, 1, 4-cyclohexanedimethanol monovinyl ether, 3-aminopropyl vinyl ether, 1, 4-butanediol divinyl ether, diethylene glycol divinyl ether, 1, 4-cyclohexanedimethanol divinyl ether, vinyl acetate, vinyl propionate, vinyl benzoate, vinyl chloroformate, vinyl cinnamate, vinyl alcohol, N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylimidazole, N-vinyl-N-methylacetamide, acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, methyl methacrylate, ethyl methacrylate, benzyl acrylate, benzyl methacrylate, acrylamide, maleic acid, N-methylmaleimide, N-ethylmaleimide, methyl maleate, ethyl maleate, allylamine, and the like. The terpolymer preferably comprises about 5 wt% to about 95 wt% CTFE monomer units, about 95 wt% to about 5 wt% VC monomer units, and about 0.5 wt% to about 30 wt% of the third monomer units. Terpolymers have improved properties, and in particular solubility, hydrophilicity, adhesion and crosslinking, for use in films, coatings, extruded articles and other applications. It will be understood by those of ordinary skill in the art to which the invention relates that any feature described herein with respect to any particular aspect and/or embodiment of the invention may be combined with one or more of any other feature in any other aspect and/or embodiment of the invention described herein, and modified as appropriate to ensure compatibility of the combination. Such combinations are considered part of the invention contemplated by this disclosure.
The following examples further illustrate the invention but are not to be construed as limiting the full scope thereof.
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