阅读说明：本技术 一种活性氧响应型的环保可降解聚氨酯材料的制备方法 (Preparation method of active oxygen response type environment-friendly degradable polyurethane material ) 是由 王文爽 陈超 于 2020-12-02 设计创作，主要内容包括：本发明公开一种活性氧响应型的环保可降解聚氨酯材料的制备方法,包括以下步骤：S1：将氨基硅烷偶联剂滴加至N,N-二甲基甲酰胺中,搅拌均匀后,加入纳米铁酸镍、纳米磷酸银,搅拌6～12h；S2：100～120℃,将聚丙二醇、聚四亚甲基醚二醇减压干燥至含水量为40～50％,再加入甲苯二异氰酸、催化剂,在65～80℃氮气气氛下,反应2～3h；S3：将活性氧响应单体溶解于二甲基亚砜中；S4：向S2所得预聚体中加入扩链剂、S1所得氨基化光催化剂,混合均匀后,再加入活性氧响应单体溶液,于70℃继续搅拌反应4～6h,烘干。本发明制出的聚氨酯材料降解周期短,且降解产物无毒无害,绿色环保,纳米铁酸镍、纳米磷酸银引入还增强了聚氨酯硬度、耐磨性和机械强度。(The invention discloses a preparation method of an active oxygen response type environment-friendly degradable polyurethane material, which comprises the following steps: s1: dropwise adding an aminosilane coupling agent into N, N-dimethylformamide, uniformly stirring, adding nano nickel ferrite and nano silver phosphate, and stirring for 6-12 h; s2: drying polypropylene glycol and polytetramethylene ether glycol under reduced pressure at 100-120 ℃ until the water content is 40-50%, adding toluene diisocyanate and a catalyst, and reacting for 2-3 hours at 65-80 ℃ in a nitrogen atmosphere; s3: dissolving an active oxygen-responsive monomer in dimethyl sulfoxide; s4: and adding a chain extender and the amination photocatalyst obtained in the step S1 into the prepolymer obtained in the step S2, uniformly mixing, adding an active oxygen response monomer solution, continuously stirring and reacting at 70 ℃ for 4-6 hours, and drying. The polyurethane material prepared by the invention has short degradation period, the degradation product is nontoxic and harmless, the polyurethane material is green and environment-friendly, and the hardness, the wear resistance and the mechanical strength of the polyurethane material are enhanced by introducing the nano nickel ferrite and the nano silver phosphate.)

1. A preparation method of an active oxygen response type environment-friendly degradable polyurethane material is characterized by comprising the following steps: the method comprises the following reaction raw materials in parts by mass:

the method specifically comprises the following steps:

s1: amination treatment of nano nickel ferrite and silver phosphate: dropwise adding an aminosilane coupling agent into N, N-dimethylformamide, uniformly stirring, adding nano nickel ferrite and nano silver phosphate, stirring for 6-12 h, and carrying out an amination reaction to prepare an amination photocatalyst;

s2: drying polypropylene glycol and polytetramethylene ether glycol under reduced pressure at 100-120 ℃ until the water content is 40-50%, adding toluene diisocyanate and a catalyst, and performing nucleophilic addition reaction for 2-3 hours at 65-80 ℃ in a nitrogen atmosphere to obtain a polyurethane prepolymer;

s3: dissolving an active oxygen response monomer in a dimethyl sulfoxide solvent to obtain an active oxygen response monomer solution;

s4: and adding a chain extender and the amination photocatalyst obtained in the step S1 into the polyurethane prepolymer obtained in the step S2, uniformly mixing, adding an active oxygen response monomer solution, continuously stirring and reacting for 4-6 hours at 70 ℃, and drying to obtain the degradable polyurethane material.

2. The preparation method of the active oxygen response type environmentally-friendly degradable polyurethane material as claimed in claim 1, wherein the active oxygen response monomer is prepared from a selenol monomer and a phenylboronic acid monomer according to the following ratio of (0.4-0.8): 1, and mixing the components in a mass ratio of 1.

3. The method for preparing the active oxygen response type environmentally-friendly degradable polyurethane material as claimed in claim 2, wherein the selenol monomer is diselenediol.

4. The method for preparing the active oxygen response type environmentally friendly degradable polyurethane material according to claim 2, wherein the phenylboronic acid monomer is 4-hydroxyphenylboronic acid.

5. The method for preparing the active oxygen response type environmentally-friendly degradable polyurethane material according to claim 1, wherein the chain extender comprises one or more of dimethylolpropionic acid, 1, 4-butanediol, 1, 6-hexanediol, N-dihydroxyethylaniline, trimethylolpropane, triethylene glycol and diethylaminoethanol.

6. The method for preparing the active oxygen response type environmentally friendly degradable polyurethane material according to claim 1, wherein the catalyst comprises one or more of dibutyltin dilaurate, stannous octoate and bismuth isooctanoate.

7. The method for preparing an active oxygen response type environmentally friendly degradable polyurethane material as claimed in claim 1, wherein the aminosilane coupling agent comprises one or more of gamma-aminopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, N-beta- (aminoethyl) -gamma-aminopropyltrimethoxysilane, N-beta- (aminoethyl) -gamma-aminopropylmethyldimethoxysilane, and 3- (phenylamino) propyltrimethoxysilane.

Technical Field

The invention belongs to the technical field of degradable polyurethane preparation, and particularly relates to a preparation method of an active oxygen response type environment-friendly degradable polyurethane material.

Background

Polyurethane is generally called polyurethane, is generated by polyisocyanate and polyol polymer through addition polymerization reaction, has the advantages of high strength, tear resistance, abrasion resistance and the like due to the fact that the main groups are urethane bonds and the secondary groups are ether, ester, urea and the like, and is widely applied to the fields of medical treatment, clothing, electrical appliances, traffic and the like. The polyurethane is a high polymer, has good durability, is not easy to degrade under natural conditions, has poor environmental protection performance, and aggravates the problem of environmental pollution.

At present, the method for improving the biodegradability of polyurethane mainly comprises the steps of introducing degradable chain segments, doping oxidant, doping photocatalyst and the like, for example, patent No. CN201711425440.1 discloses degradable aliphatic polycarbonate/polyurethane copolymerized foaming material and preparation thereof, for example, patent with application number CN201710579612.4 discloses an environment-friendly water-based polyurethane resin based on degradable biological base and a preparation method thereof, for example, CN201410012053.5 discloses a preparation method of polylactic acid-based degradable polyurethane foam, for example, patent No. CN201610200126.2 discloses a degradable polyurethane material with high mechanical property based on isosorbide and polylactic acid and a synthesis method thereof, for example, patent with application number CN201610327590.8 discloses a preparation method of degradable aqueous polyurethane paint and a product thereof, for example, CN201210037517.9 discloses a degradable polyurethane plastic using phosphorus pentoxide. However, there are few studies and reports on the preparation method of an active oxygen responsive environmentally friendly degradable polyurethane material.

In order to further develop an environment-friendly novel environment-friendly degradable polyurethane material, the invention firstly utilizes selenol monomer, phenylboronic acid monomer, amination photocatalyst, toluene diisocyanate, polypropylene glycol and polytetramethylene ether glycol for graft copolymerization to prepare the active oxygen response type and visible light response type polyurethane material, and the polyurethane material can be rapidly degraded in nature and is environment-friendly.

Disclosure of Invention

Aiming at the defects of the prior art, the invention aims to provide a preparation method of an active oxygen response type degradable polyurethane material.

The technical scheme of the invention is summarized as follows:

a preparation method of an active oxygen response type environment-friendly degradable polyurethane material comprises the following reaction raw materials in parts by mass:

the method specifically comprises the following steps:

s1: amination treatment of nano nickel ferrite and silver phosphate: dropwise adding an aminosilane coupling agent into N, N-dimethylformamide, uniformly stirring, adding nano nickel ferrite and nano silver phosphate, stirring for 6-12 h, and carrying out an amination reaction to prepare an amination photocatalyst;

s2: drying polypropylene glycol and polytetramethylene ether glycol under reduced pressure at 100-120 ℃ until the water content is 40-50%, adding toluene diisocyanate and a catalyst, and performing nucleophilic addition reaction for 2-3 hours at 65-80 ℃ in a nitrogen atmosphere to obtain a polyurethane prepolymer;

s3: dissolving an active oxygen response monomer in a dimethyl sulfoxide solvent to obtain an active oxygen response monomer solution;

s4: and adding a chain extender and the amination photocatalyst obtained in the step S1 into the polyurethane prepolymer obtained in the step S2, uniformly mixing, adding an active oxygen response monomer solution, continuously stirring and reacting for 4-6 hours at the temperature of 70 ℃, drying and removing dimethyl sulfoxide and N, N-dimethylformamide to obtain the degradable polyurethane material.

Preferably, the active oxygen response monomer is prepared from a selenol monomer and a phenylboronic acid monomer according to the weight ratio of (0.4-0.8): 1, and mixing the components in a mass ratio of 1.

Preferably, the selenol monomer is diselenediol.

Preferably, the phenylboronic acid monomer is 4-hydroxyphenylboronic acid.

Preferably, the chain extender comprises one or more of dimethylolpropionic acid, 1, 4-butanediol, 1, 6-hexanediol, N-dihydroxyethylaniline, trimethylolpropane, triethylene glycol, diethylaminoethanol.

Preferably, the catalyst comprises one or more of dibutyltin dilaurate, stannous octoate, bismuth isooctanoate.

Preferably, the aminosilane coupling agent comprises one or more of gamma-aminopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, N-beta- (aminoethyl) -gamma-aminopropyltrimethoxysilane, N-beta- (aminoethyl) -gamma-aminopropylmethyldimethoxysilane, 3- (phenylamino) propyltrimethoxysilane.

The invention has the beneficial effects that:

1. the invention firstly utilizes selenol monomer, phenylboronic acid monomer, amination photocatalyst and toluene diisocyanate, polypropylene glycol and polytetramethylene ether glycol for graft copolymerization, active oxygen response monomer carries out graft reaction with-NCO in polyurethane prepolymer through-OH functional group, amination photocatalyst passes through-NH₂Functional groups and-NCO are subjected to grafting reaction, and then diselenide and 4-hydroxyphenylboronic acid active oxygen response blocks are inserted into a polyurethane main chain, nano nickel ferrite and nano silver phosphate are introduced into a polyurethane structural chain, so that the polyurethane has an excellent visible light catalytic effect, photo-generated cavities generated by the nano nickel ferrite and the nano silver phosphate under the action of sunlight further react with water molecules in the air to generate active oxygen radicals such as hydroxyl free radicals and superoxide free radicals, the active oxygen radicals are transferred to the diselenide and 4-hydroxyphenylboronic acid response blocks in the polyurethane, the diselenide blocks are oxidized into selenic acid, the diselenide bonds are broken, the 4-hydroxyphenylboronic acid blocks are oxidized into phenol and boric acid, the breaking of the polyurethane macromolecular chain is further realized, the polyurethane is rapidly degraded, and the boric acid products are used for the polyurethaneThe self-degradation of the urethane has a further catalytic effect.

2. The polyurethane material prepared by the invention has short degradation period, and the degradation product is non-toxic and harmless, and is green and environment-friendly.

3. The introduction of the nano nickel ferrite and the nano silver phosphate can also improve the strength of a polyurethane macromolecular skeleton, and enhance the hardness, the wear resistance and the mechanical strength of polyurethane.

Drawings

FIG. 1 is a flow chart of a preparation method of the active oxygen response type environmentally-friendly degradable polyurethane material.

Detailed Description

The present invention is further described in detail below with reference to examples so that those skilled in the art can practice the invention with reference to the description.

Example 1

A preparation method of an active oxygen response type environment-friendly degradable polyurethane material comprises the following reaction raw materials in parts by mass:

the active oxygen response monomer is prepared from diselenediol and 4-hydroxyphenylboronic acid according to a weight ratio of 0.4: 1 by mass ratio;

the method specifically comprises the following steps:

s1: amination treatment of nano nickel ferrite and silver phosphate: dripping gamma-aminopropyl trimethoxy silane into N, N-dimethylformamide, uniformly stirring, adding nano nickel ferrite and nano silver phosphate, stirring for 6 hours, and carrying out an amination reaction to prepare an amination photocatalyst;

s2: drying polypropylene glycol and polytetramethylene ether glycol under reduced pressure at 100 ℃ until the water content is 40-50%, adding toluene diisocyanate and toluene diisocyanate, and carrying out nucleophilic addition reaction for 2h at 70 ℃ in a nitrogen atmosphere to obtain a polyurethane prepolymer;

s3: dissolving an active oxygen response monomer in a dimethyl sulfoxide solvent to obtain an active oxygen response monomer solution;

s4: and (2) adding dimethylolpropionic acid and the amination photocatalyst obtained in S1 into the polyurethane prepolymer obtained in S2, uniformly mixing, adding an active oxygen response monomer solution, continuously stirring and reacting for 4 hours at 70 ℃, drying and removing dimethyl sulfoxide and N, N-dimethylformamide to obtain the degradable polyurethane material.

Example 2

A preparation method of an active oxygen response type environment-friendly degradable polyurethane material comprises the following reaction raw materials in parts by mass:

the active oxygen response monomer is prepared from diselenediol and 4-hydroxyphenylboronic acid according to a weight ratio of 0.6: 1 by mass ratio;

the method specifically comprises the following steps:

s1: amination treatment of nano nickel ferrite and silver phosphate: dropwise adding N-beta- (aminoethyl) -gamma-aminopropyltrimethoxysilane into N, N-dimethylformamide, uniformly stirring, adding nano nickel ferrite and nano silver phosphate, stirring for 10 hours, and carrying out an amination reaction to prepare an amination photocatalyst;

s2: drying polypropylene glycol and polytetramethylene ether glycol under reduced pressure at 110 ℃ until the water content is 45%, adding toluene diisocyanate and stannous octoate, and performing nucleophilic addition reaction for 3 hours at 75 ℃ in a nitrogen atmosphere to obtain a polyurethane prepolymer;

s3: dissolving an active oxygen response monomer in a dimethyl sulfoxide solvent to obtain an active oxygen response monomer solution;

s4: and adding 1, 4-butanediol and the amination photocatalyst obtained from S1 into the polyurethane prepolymer obtained from S2, uniformly mixing, adding an active oxygen response monomer solution, continuously stirring and reacting for 5 hours at 70 ℃, drying and removing dimethyl sulfoxide and N, N-dimethylformamide to obtain the degradable polyurethane material.

Example 3

A preparation method of an active oxygen response type environment-friendly degradable polyurethane material comprises the following reaction raw materials in parts by mass:

the active oxygen response monomer is prepared from diselenediol and 4-hydroxyphenylboronic acid according to a weight ratio of 0.8: 1 by mass ratio;

the method specifically comprises the following steps:

amination treatment of nano nickel ferrite and silver phosphate: dropwise adding N-beta- (aminoethyl) -gamma-aminopropylmethyldimethoxysilane into N, N-dimethylformamide, uniformly stirring, adding nano nickel ferrite and nano silver phosphate, stirring for 12h, and carrying out amination reaction to prepare an amination photocatalyst;

s2: drying polypropylene glycol and polytetramethylene ether glycol under reduced pressure at 120 ℃ until the water content is 50%, adding toluene diisocyanate and dibutyltin dilaurate, and performing nucleophilic addition reaction for 3 hours at 80 ℃ in a nitrogen atmosphere to obtain a polyurethane prepolymer;

s3: dissolving an active oxygen response monomer in a dimethyl sulfoxide solvent to obtain an active oxygen response monomer solution;

s4: adding diethylaminoethanol and the amination photocatalyst obtained in the step S1 into the polyurethane prepolymer obtained in the step S2, uniformly mixing, adding an active oxygen response monomer solution, continuously stirring and reacting for 6 hours at the temperature of 70 ℃, drying and removing dimethyl sulfoxide and N, N-dimethylformamide to obtain the degradable polyurethane material.

Comparative example 1: the same as in example 1, except that: comparative example 1 contained no active oxygen-responsive monomer.

Comparative example 2: the same as in example 1, except that: the comparative example 2 does not contain nano nickel ferrite and nano silver phosphate.

Comparative example 3: the same as in example 1, except that: comparative example 3 does not contain active oxygen responsive monomer, nor does it contain nano nickel ferrite and nano silver phosphate.

Degradation test:

the polyurethanes of examples 1 to 3 and comparative examples 1 to 3 were weighed respectively5.0g of ester material, simulated by a 500W xenon lamp transmission filter, with the light intensity of 80mW/cm²Continuously irradiating with light at 7d, 15d, 30d and 45d under the condition of air humidity of 95%, and measuring M₇、M₁₅、M₃₀、M₄₅According to the formula 100% × (5.0-M)₇/M₁₅/M₃₀/M₄₅) The degradation rate was calculated at 5.0 and the test results are shown in the following table:

	7d	15d	30d	45d
					example 1	8.8	20.3	47.5	61.8
Example 2	10.4	23.5	53.7	69.5
					Example 3	12.2	27.1	60.4	75.2
Comparative example 1	4.6	12.0	27.3	41.5
					Comparative example 2	5.8	14.9	25.5	36.1
Comparative example 3	3.5	7.6	17.2	26.4

As can be seen from the above table, in 7-15 days, the influence degree of the active oxygen response monomer on the degradation of the polyurethane material is greater than that of the nano nickel ferrite and the nano silver phosphate, along with the continuous disintegration of the active oxygen response monomer in a polyurethane molecular chain, the polyurethane molecular chain is broken into small molecular chains, but the content of an active oxygen response block is continuously reduced, the degradation speed is slowed down and tends to be stable, and in 30-45 days, the influence degree of the nano nickel ferrite and the nano silver phosphate on the degradation of the polyurethane material is greater than that of the active oxygen response monomer.

Examples 1 to 3 graft copolymerization of a selenol monomer, a phenylboronic acid monomer, an amination catalyst, toluene diisocyanate, polypropylene glycol, and polytetramethylene ether glycol for the first time, an active oxygen-responsive monomer was graft-reacted with-NCO in a polyurethane prepolymer via an-OH functional group, and an amination catalyst was graft-reacted with-NH₂The functional group and-NCO are subjected to grafting reaction, and then diselenediol and 4-hydroxy phenylboronic acid active oxygen are subjected to reactionThe response block is inserted into a polyurethane main chain, nano nickel ferrite and nano silver phosphate are introduced into a polyurethane structural chain, so that the polyurethane has an excellent visible light catalytic effect, under the action of sunlight, generated photoproduction cavities further react with water molecules in the air to generate active oxygen free radicals such as hydroxyl free radicals and superoxide free radicals, the active oxygen free radicals are transferred to the diselenediol and the 4-hydroxyphenylboronic acid response block in the polyurethane, the diselenediol block is oxidized into selenic acid, so that the diselenic bond is broken, the 4-hydroxyphenylboronic acid block is oxidized into phenol and boric acid, further, the breaking of a polyurethane macromolecular chain is realized, the polyurethane is rapidly degraded, and the boric acid product has a further catalytic effect on the self-degradation of the polyurethane.

The polyurethane materials prepared in the embodiments 1-3 have short degradation period, and degradation products are non-toxic, harmless, green and environment-friendly.

The introduction of the nano nickel ferrite and the nano silver phosphate in the embodiments 1 to 3 can also improve the strength of the polyurethane macromolecular skeleton, and can enhance the hardness, the wear resistance and the mechanical strength of the polyurethane.

While embodiments of the invention have been disclosed above, it is not limited to the applications listed in the description and the embodiments, which are fully applicable in all kinds of fields of application of the invention, and further modifications may readily be effected by those skilled in the art, so that the invention is not limited to the specific details without departing from the general concept defined by the claims and the scope of equivalents.