Amorphous polyester composition and method for producing same
阅读说明：本技术 无定形聚酯组合物及其制造方法 (Amorphous polyester composition and method for producing same ) 是由 M·A·巴格尔 S·科斯特 M·E·波特 P·海德尔 于 2020-03-27 设计创作，主要内容包括：无定形聚酯或共聚酯组合物包含结晶或半结晶聚酯或共聚酯(任选地来源于再循环的废物流)、至少一种二醇或芳族二酸或二酸的酯或羟基羧酸或内酯或二酐、以及催化剂的反应产物,其中所述无定形组合物具有如通过凝胶渗透色谱法测量的至少10,000g/mol的重均分子量(聚苯乙烯当量分子量)。(An amorphous polyester or copolyester composition comprises the reaction product of a crystalline or semi-crystalline polyester or copolyester (optionally derived from a recycled waste stream), at least one diol or aromatic diacid or ester of a hydroxycarboxylic acid or lactone or dianhydride, and a catalyst, wherein the amorphous composition has a weight average molecular weight (polystyrene equivalent molecular weight) of at least 10,000g/mol as measured by gel permeation chromatography.)
1. An amorphous polyester or copolyester composition comprising
Crystalline or semi-crystalline polyesters or copolyesters-optionally originating from a recycled waste stream,
at least one diol or aromatic diacid or ester of diacid or hydroxycarboxylic acid or lactone or dianhydride, and
the reaction products of the catalyst are formed by reacting the catalyst,
wherein the amorphous composition has a weight average molecular weight-polystyrene equivalent molecular weight of at least 10,000g/mol as measured by gel permeation chromatography.
2. The amorphous composition of claim 1, wherein the polyester is polyethylene terephthalate, or a polyester, wherein the primary diol component is ethylene glycol, propylene glycol, 1, 4-butanediol, spiroglycol, or blends thereof.
3. The amorphous composition of claim 1, wherein the at least one aromatic diacid monomer is phthalic acid, terephthalic acid, isophthalic acid, or 2, 5-furandicarboxylic acid, or a combination thereof.
4. The amorphous composition of claim 1, wherein the at least one diol is ethylene glycol, 1, 2-propanediol, 1, 3-propanediol, butanediol, 1, 4-butanediol, spiroglycol, isosorbide, cyclohexanedimethanol, or cyclobutanediol, or a combination thereof.
5. Amorphous composition according to claim 1, wherein the catalyst is or comprises titanium tetrabutoxide, cerium (III) acetate, tetraisopropyl titanate, antimony trioxide or organometallic complexes based on tin.
6. The amorphous composition of claim 1, having a Tg of at least 75 ℃.
7. An amorphous composition according to claim 4 wherein the cyclohexanedimethanol is 1, 4-cyclohexanedimethanol and is present in an amount of 20 to 40 mole% of the total diol content.
8. The amorphous composition according to claim 4, wherein the isosorbide is present in an amount of 15 to 100 mole% of the total diol content.
9. The amorphous composition of claim 4, wherein the cyclobutanediol is 2-2-4-4-tetramethyl-1-3-cyclobutanediol is present in an amount from 45 to 55 mole% of the total diol content.
10. The amorphous composition according to claim 4 wherein the cyclohexanedimethanol is 1,3 cyclohexanedimethanol, 1,4 cyclohexanedimethanol, or blends thereof, present in an amount of 20 to 30 mole percent and when combined with isophthalic or terephthalic acid, or blends thereof, present in an amount of 20 to 30 mole percent.
11. A foamable composition comprising the amorphous polyester or copolyester resin of claim 1 and one or more blowing agents.
12. The foamable composition of claim 11 wherein the foamable composition is in the form of solid beads.
13. The foamable composition of claim 11 wherein the blowing agent is selected from one or more pentanes, one or more halogenated hydrocarbons, one or more hydrofluorocarbons, alcohols, ketones, ethers, olefins, carbon dioxide, water, or combinations thereof.
14. A foamed article made by extrusion foaming of the foamable composition of claim 11 or expansion of the solid beads of claim 12, wherein the article has no greater than 96kg/m3(6 pcf).
15. A method of preparing an amorphous polyester foamable resin composition, said method comprising the steps of:
combining a crystalline or semi-crystalline polyester-optionally originating from a recycled waste stream-with at least one diol or aromatic diacid or ester of diacid or hydroxycarboxylic acid or lactone or dianhydride in a reactor at room temperature and in the presence of a catalyst,
the reactor was sealed and purged with an inert gas,
the contents are mixed together and the mixture is stirred,
discharging the volatile components from the reactor,
flushing the reactor with an inert gas at least once,
increasing the temperature of the reactor to 250-350 ℃ over a period of 30 to 90 minutes,
the combination of the molten materials is mixed and,
the temperature is kept between 250 ℃ and 350 ℃ for 20 to 150 minutes,
the reactor was evacuated to negative 25 inches of mercury or less,
the reaction is continued at a temperature of 250-350 deg.C for 100 to 300 minutes, optionally while removing volatiles through a distillation column, and
stopping the reaction by stopping mixing, purging the reactor with an inert gas, returning the reactor to atmospheric pressure, and reducing the temperature to 100 degrees Celsius or less,
wherein the resulting composition has a weight average molecular weight (polystyrene equivalent molecular weight) of at least 10,000g/mol as measured by gel permeation chromatography) and a crystallinity of no greater than 5% as determined by differential scanning calorimetry.
Technical Field
Described herein is a composition and process for making an amorphous polyester composition that can be converted into a low density foam suitable for use as insulation for construction and other industrial applications.
Background
Crystalline and semi-crystalline polyester polymers cannot be easily foamed to produce low density foams because their crystalline or semi-crystalline nature means that high temperatures are required to prevent recrystallization of the material as the entrapped gas expands and produces a foam. In the molten state, above its recrystallization temperature, the viscosity and melt strength of semi-crystalline polyesters such as PET are too low to allow the cells to expand significantly before hardening. This limits the foam density that can be achieved (to foams of higher density, for example, characterized by greater than 96kg/m3(6 pcf). The present invention solves the problem of foaming crystalline or semi-crystalline polyesters to produce low density foams by converting crystalline or semi-crystalline polyesters such as polyethylene terephthalate (PET) into amorphous copolyester polymeric materials capable of producing low density foams from polymer melts or extruded expandable beads containing a suitable blowing agent.
In the production of foamable polyesters or copolyesters derived from semi-crystalline PET, the starting materials may be obtained as virgin materials or from "recycled" waste streams, such as PET bottles and other post-consumer PET sources. For the purposes of the present invention, "recycled" refers to materials obtained after consumption and after industrial use. Accordingly, one particularly desirable goal is to utilize recycled semi-crystalline PET and convert it to an amorphous, less crystalline polymer that can be foamed to produce a low density foam. Accordingly, there is a need for foamable compositions (virgin or recycled) containing amorphous polymers derived from crystalline or semi-crystalline polyesters, processes for preparing amorphous polymers and foamable compositions, and methods of using the same. The present invention is directed to these and other important ends.
Disclosure of Invention
An amorphous polyester or copolyester composition comprises the reaction product of a crystalline or semi-crystalline polyester or copolyester (optionally derived from a recycled waste stream), at least one diol or aromatic diacid or ester of a hydroxycarboxylic acid or lactone or dianhydride, and a catalyst, wherein the amorphous composition has a weight average molecular weight (polystyrene equivalent molecular weight) of at least 10,000g/mol as measured by gel permeation chromatography.
A method of making an amorphous polyester resin as described herein comprises the steps of:
combining a crystalline or semi-crystalline polyester (optionally derived from a recycled waste stream) with at least one diol or aromatic diacid or ester of a diacid or hydroxycarboxylic acid or lactone or dianhydride in a reactor at room temperature and in the presence of a catalyst,
the reactor was sealed and purged with an inert gas,
the contents are mixed together and the mixture is stirred,
the volatile components in the reactor are discharged,
the reactor is flushed at least once with an inert gas,
increasing the temperature of the reactor to 250-350 ℃ over a period of 30 to 90 minutes,
the combination of molten materials is mixed and,
the temperature is maintained between 250 ℃ and 350 ℃,
the reactor was evacuated to negative 25 inches of mercury or less,
the reaction is continued at a temperature of 250 ℃ to 350 ℃ for 100 to 300 minutes, optionally while volatile substances are removed by means of a distillation column, and
the reaction is stopped by stopping the mixing, purging the reactor with an inert gas, returning the reactor to atmospheric pressure, and reducing the temperature to 100 degrees celsius or less, wherein the resulting composition has a weight average molecular weight (polystyrene equivalent molecular weight) of at least 10,000g/mol as measured by gel permeation chromatography and a crystallinity of no greater than 5% as determined by differential scanning calorimetry.
Detailed Description
In the case of semi-crystalline PET, where the polymer consists essentially of ethylene terephthalate repeat units, the foaming must be carried out above the crystallization temperature. For PET, the temperature mapRanging from a normal melting point (about 250 ℃) to the onset temperature of crystallization of PET upon cooling from the molten state (about 150 ℃), as determined by Differential Scanning Calorimetry (DSC) at a heating and cooling rate of 10 ℃/min. At such high temperatures, molten PET has very low melt strength and only minimal expansion before crystallization-induced vitrification begins. As disclosed herein, PET (virgin or recycled) becomes an amorphous, less crystalline form. The elimination of crystallization allows the polymer to be melt processed below 150 c, where both melt strength and viscosity are higher. This helps the cells expand and restricts cell coalescence, thereby enabling the production of a low density foamed product. However, although it is necessary to eliminate the crystallinity in the pure form of the polymer, it is not sufficient to achieve foamability. The addition of one or more soluble blowing agents will increase the crystallization rate. Further specifically disclosed herein are types of polymer chain structures that are required to sufficiently reduce the rate of crystallization in the presence of such blowing agents (such as, for example, carbon dioxide) to facilitate foaming. This is an essential property of the polymer to be properly foamable at temperatures below 150 ℃ to achieve less than 96kg/m3(6pcf), more preferably less than 80kg/m3(5pcf), and even more preferably less than 40kg/m3(2.5 pcf).
Unlike semi-crystalline PET, which is known to have poor solubility for typical blowing agents, the process of the present invention modifies PET to produce an amorphous polymer having higher solubility for typical blowing agents and allows for the production of low density foam articles. Preventing the formation of crystalline structures also increases gas permeability, which facilitates cell growth during foam processing.
Both virgin and recycled PET can be used for foaming by reducing or eliminating its ability to crystallize in the presence of heat and/or dissolved gases. This is achieved by: molten PET is subjected to direct transesterification with one or more monomers in the presence of a catalyst to promote rearrangement of the type and order of the repeating units contained in the polymer to form a new random copolyester. The new monomer component may include organic esters, diols, diacids, dianhydrides, hydroxycarboxylic acids, or lactones. The composition may include a polyol, polyacid or polyanhydride, or other multifunctional species intended to introduce long chain branching. Since esterification is an equilibrium reaction, continuous removal of water or alcohol or ethylene glycol may be required to drive the transesterification reaction to high conversion. By appropriate selection of reaction conditions, such as catalyst, temperature, reaction time and application of vacuum, the resulting polymer has a sufficiently slow crystallization rate. This reduction or elimination of crystallization allows processing at temperatures below 150 ℃ (typical crystallization onset temperature of the starting PET material). The final copolyester may be melt blended with a physical blowing agent and expanded by extrusion foaming, or rapidly cooled and pelletized to form beads for subsequent expansion.
The term "polyester" herein refers to a polymer whose repeating units are characterized by ester groups in the polymer backbone. Thus, the term includes not only typical polyesters prepared from one diacid component and one dihydroxy component, but also esters of diacids, or hydroxycarboxylic acids, lactone-based polyesters, or dianhydrides, and copolymers, i.e. polyesters ("copolyesters") consisting of at least two acid components and/or alcohol components, and/or a hydroxycarboxylic acid component and/or lactone component. The term "copolyester" is a subset of polyesters.
As used herein, the term "foam" means a low density matrix of fluid or solid containing a plurality of finely divided voids or bubbles. The foam may be closed cell or open cell, as these terms are well known in the art. Herein, depending on the context, the term may refer to an initial foam formed from a molten polymer, or may be used to describe a final cured foam. With respect to determining whether a sample can be successfully foamed ("foamable resin" or "foamable composition"), the initial or molten sample must be foamed (by a particular process and/or under particular conditions) and be capable of forming a stable foam. The foamed article may further comprise one or more additives in any combination. Exemplary additives include infrared attenuating agents (e.g., carbon black, graphite, metal flakes, titanium dioxide); clays, such as natural absorbent clays (e.g., kaolin and montmorillonite) and synthetic clays; nucleating agents (e.g., talc and magnesium silicate); flame retardants (e.g., brominated flame retardants such as hexabromocyclododecane and brominated polymers and copolymers, phosphorus flame retardants such as triphenyl phosphate, and flame retardant packages that may include synergists (e.g., such as dicumyl and polycumyl)); lubricants (e.g., calcium stearate and barium stearate); and acid scavengers (e.g., magnesium oxide and tetrasodium pyrophosphate). Preferably, the thermoplastic polymer foam article contains an infrared attenuating agent to minimize thermal conductivity through the article. The additives are typically dispersed in a polymer matrix, usually in a continuous thermoplastic polymer phase, and are present at concentrations of up to 15 weight percent based on the total weight of polymers in the polymeric foam article.
As used herein, "stable foam" refers to a foam that is stable against observable shrinkage or collapse during the curing process and in the absence of any external forces other than the surrounding atmosphere.
As used herein, the term "rigid foam" refers to a cured foam having a cell structure with a compressive strength greater than 5 psi.
All molecular weights disclosed herein and other values related to molecular weight (e.g., polydispersity index, etc.) are measured by GPC.
As used herein, the term "number average molecular weight"Refers to the statistical average molecular weight of all polymer chains in the sample and is defined by the formula:
where Mi is the molecular weight of the chain and Ni is the number of chains with that molecular weight. The Mn of the polymer can be determined by methods well known to those of ordinary skill in the art using molecular weight standards (e.g., polystyrene standards, preferably certified or traceable molecular weight standards).
As used herein, the term "weight average molecular weight"Is defined by the formula:
where Mi is the molecular weight of the chain and Ni is the number of chains with that molecular weight. In contrast to Mn, Mw takes into account the molecular weight of a given chain in determining the contribution to the molecular weight average. Thus, the greater the molecular weight of a given chain, the greater the contribution of that chain to the Mw. The Mw of a polymer, such as a polystyrene polymer, can be determined by methods well known to those of ordinary skill in the art using molecular weight standards, such as polystyrene or poly (methyl methacrylate) standards, preferably certified or traceable molecular weight standards.
Amorphous polyester or copolyester resins
The amorphous polyester or copolyester composition comprises the reaction product of: crystalline or semi-crystalline polyesters or copolyesters, optionally from recycled waste streams,
at least one diol or aromatic diacid or ester of diacid or hydroxycarboxylic acid or lactone or dianhydride,
and a catalyst,
wherein the amorphous polymer reaction product has a weight average molecular weight of at least 10,000g/mol (polystyrene equivalent molecular weight) as measured by gel permeation chromatography.
In some embodiments, the polyester is polyethylene terephthalate, or a polyester in which the primary diol component is ethylene glycol, propylene glycol, 1, 4-butanediol, spiroglycol, or blends thereof.
In some embodiments, the at least one aromatic diacid monomer is phthalic acid, terephthalic acid, isophthalic acid, or 2, 5-furandicarboxylic acid, or a combination thereof.
In some embodiments, the at least one diol is isosorbide, cyclohexanedimethanol, or cyclobutanediol. In some such embodiments, the cyclohexanedimethanol is 1, 4-cyclohexanedimethanol, present in an amount from 20 to 40 mole% of the total diol content; isosorbide is present in an amount of 15 to 100 mol% of the total diol content; cyclobutanediol is 2-2-4-4-tetramethyl-1-3-cyclobutanediol and is present in an amount from 45 to 55 mole% of the total diol content.
In an embodiment, the cyclohexanedimethanol is 1,3 cyclohexanedimethanol, 1,4 cyclohexanedimethanol, or blends thereof, present in an amount of 20 to 30 mole%, when combined with isophthalic acid, in an amount of 20 to 30 mole%.
Suitable catalysts for the transesterification reaction include those known in the art, in particular organometallic complexes, such as, for example, titanium tetrabutoxide, Ti (OBu)4Cerium (III) acetate, Ce (OAc)3Tetraisopropyl titanate, and the same under the trade nameThe tin-based organometallic complexes available to catalysis (PMC organometallic compounds, laurshan, nj, usa). A preferred catalyst is antimony trioxide. Suitable use levels may vary from catalyst to catalyst, but are typically from 50ppm to 10,000ppm, or from 1,000ppm to 5,000ppm, or from 1,500ppm to 3,000ppm (parts by weight of catalyst per million parts of total polymer present in the reaction).
Preferably, the amorphous resin has a crystallinity of no greater than 5%, or even no greater than 1%, a maximum heat of fusion of less than 7J/g, or even less than 1J/g. The resin also has a glass transition temperature (Tg) of at least 75 ℃, or at least 85 ℃, or at least 90 ℃, or at least 100 ℃, or at least 110 ℃.
Process for preparing amorphous polyester or copolyester resins
A method of making an amorphous polyester resin as described herein comprises the steps of:
combining a crystalline or semi-crystalline polyester (optionally derived from a recycled waste stream) with at least one diol or aromatic diacid or ester of a diacid or hydroxycarboxylic acid or lactone or dianhydride in a reactor at room temperature and in the presence of a catalyst,
the reactor was sealed and purged with an inert gas,
mixing the contents, discharging the volatile components in the reactor,
the reactor is flushed at least once with an inert gas,
increasing the temperature of the reactor to 250 ℃ -350 ℃, such as 280 ℃ -290 ℃ or 283 ℃ -287 ℃,
such as mixing the combination of molten materials at a rate of 100-200rpm,
maintaining the temperature at 250-350 ℃, such as 280-290 ℃ or 283-287 ℃, for a time period of 20-200 minutes, or 20-150 minutes or 40-100 minutes,
the reactor was evacuated to negative 25 inches of mercury or less,
continuing the reaction at a temperature of 250 ℃ -350 ℃, or 280 ℃ -290 ℃, or 283 ℃ -287 ℃ for 100 to 300 minutes or 200 to 220 minutes, 208 to 212 minutes, optionally while removing volatile substances, e.g. by a distillation column, and
the reaction is stopped by stopping the mixing, purging the reactor with an inert gas, returning the reactor to atmospheric pressure and reducing the temperature to 100 degrees celsius or less,
wherein the resulting composition has a weight average molecular weight (polystyrene equivalent molecular weight as measured by gel permeation chromatography) of at least 10,000g/mol and a crystallinity as determined by differential scanning calorimetry of no greater than 5%, or no greater than 1%.
In some embodiments, the holding time is 40-50 minutes or even 43-47 minutes. In other embodiments, the holding time is 80-100 minutes, more preferably 85-95 minutes, or most preferably 87-93 minutes.
An alternative method of preparing amorphous polyester resin comprises the steps of:
combining a crystalline or semi-crystalline polyester (optionally derived from a recycled waste stream) with at least one diol or aromatic diacid or ester of a diacid or hydroxycarboxylic acid or lactone or dianhydride in a reactor at room temperature and in the presence of a catalyst,
the reactor was sealed and purged with an inert gas,
the contents are mixed together and the mixture is stirred,
the volatile components in the reactor are discharged,
the reactor is flushed at least once with an inert gas,
increasing the temperature of the reactor to 250-350 ℃, or 280-290 ℃, or 283-287 ℃ over a period of 30 to 90 minutes, or 50 to 70 minutes, preferably 55-65 minutes, or even 58-63 minutes,
such as mixing the combination of molten materials at a rate of 100-200rpm,
the temperature is maintained at 250-350 ℃ or 280-290 ℃, preferably 283-287 ℃, for a time period of 20-150 minutes or 40-100 minutes,
the reactor was evacuated to negative 25 inches of mercury or less,
the reaction is continued at a temperature of 250 ℃ to 350 ℃ or 280 ℃ to 290 ℃, preferably 283 ℃ to 287 ℃ for 100 to 300 minutes, or 200 to 220 minutes, preferably 208 ℃ to 212 minutes, optionally while removing volatile substances, for example by means of a distillation column,
by stopping mixing, purging the reactor with inert gas, returning the reactor to atmospheric pressure, and,
the molten or optionally solidified product is transferred to a continuous melt processing apparatus (such as a single or twin screw extruder) capable of heating, mixing, and exposing the molten product to reduced pressure in order to remove volatile materials and maintain the product in a molten state.
The resulting composition has a weight average molecular weight (polystyrene equivalent molecular weight as measured by gel permeation chromatography) of at least 10,000g/mol and a crystallinity as determined by differential scanning calorimetry of no greater than 5%, or no greater than 1%.
In some embodiments, a second polymeric substance may be added to the melt processing apparatus in addition to the polyester resin product.
Some embodiments disclosed herein are set forth in the claims, and any combination of these embodiments (or portions thereof) can be made to define an embodiment.
Foamable compositions
In an embodiment, a foamable composition is provided comprising an amorphous polyester or copolyester resin as described above and one or more blowing agents. In certain embodiments, the blowing agent is selected from one or more physical blowing agents, such as pentane, hydrofluoroolefins, carbon dioxide, nitrogen, oxygen, water, alcohols (such as methanol and ethanol), ketones (including acetone), ethers (such as dimethyl ether or diethyl ether), halogenated hydrocarbons (such as vinyl chloride or methylene chloride), or olefins (such as pentene), or combinations thereof. Examples of suitable chemical blowing agents are azides such as Azodicarbonamide (AZNP), 5-phenyltetrazole (5PT), or a mixture of citric acid and bicarbonate.
Solid expandable beads
In another embodiment of the present invention, there is provided solid foamable beads made from the foamable compositions disclosed herein.
Foamed article
Furthermore, the present invention provides a foamed article comprising a foamable composition as described above, said article being made by any of the following processes: (a) extrusion expansion of any foamable composition, or (b) bead expansion of solid foamable beads as described above. Extrusion foaming and bead expansion are well known terms in the art of foamed articles. In some embodiments, the foamed article has no greater than 96kg/m3(6pcf), or not more than 80kg/m3(5pcf), or not more than 40kg/m3(2.5 pcf).
Test method
Differential Scanning Calorimetry (DSC) method a:the sample was heated at a rate of 10 ℃/min from 30 ℃ to 300 ℃ under a nitrogen atmosphere and then cooled back to 30 ℃ at 10 ℃/min. The sample was then heated a second time from 30 ℃ to 300 ℃ at 10 ℃/min. The second heating scan was used to measure the glass transition temperature (Tg) and any heat of fusion (Tm) associated with crystallinity. The inflection point is used to designate Tg. The Tm is determined by integrating any region representing the baseline deviation from 175 ℃ to 225 ℃. In attempting to foamBefore and after, the method was used for all examples.
Gel Permeation Chromatography (GPC) method B:the sample was dissolved at 40mg/ml in Hexafluoroisopropanol (HFIP). After 24 hours shaking at room temperature, the sample was completely dissolved in HFIP. Once dissolved in HFIP, the sample was diluted to 2mg/ml with chloroform and filtered through a 0.2um PTFE filter. The sample was then passed through a pair of mixed C GPC columns at 1ml/min in chloroform mobile phase. The injection volume was 50 microliters and the temperature was maintained at 35 ℃. UV (263nm) and IR detectors were used for detection, and a series of Polystyrene (PS) molecular weight standards were used for molecular weight calibration. All reported molecular weights are PS equivalent molecular weights.
Foam density measurement:this was determined according to ASTM method D-1622-03.
Foamability evaluation method C:to evaluate the foamability of the comparative examples and examples of the present invention, the samples were compression-molded into 1.3mm thick films (5 minutes at 180 ℃ C. under a pressure of 25 tons). A portion of the pressed film (area about 7mm x 7mm) was placed in a pressure vessel preheated to 125 ℃. The vessel was then pressurized to 1000psi using carbon dioxide and the sample was allowed to soak for 3-4 hours to dissolve the gas into the polymer. The pressure was then released rapidly to induce foaming in the sample. Successful foaming was determined by visual observation of void formation in the polymer sample and a corresponding increase in sample volume of at least 50%.
Examples of the invention
Comparative example a:
semi-crystalline PET (Certene 8080 from Muehlstein) was pressed into a film and tested for foamability using the method described above, except that the pressing temperature was 280 ℃. After depressurization, the volume of the sample did not increase and a very opaque white appearance was observed. The DSC of the sample was found to contain a significant melting peak (>20J/g) indicating crystallinity.
Comparative example B:
amorphous PET (Altester 45 supplied by Mitsubishi Gas Chemical) was pressed into a film and tested using the method described aboveFoamability, except that only 800psi of CO is used2And the soaking time was 12 hours. After depressurization, no increase in volume of the sample was observed and the sample had a very opaque white appearance. The DSC of the sample was found to contain a significant melting peak (>Heat of fusion of 20J/g).
Example 1: reaction of polyesters with cyclohexanedimethanol and terephthalic acid
Virgin poly (ethylene terephthalate) (10g) supplied by Muehlstein corporation was added to a 100ml glass reactor at room temperature. Next, an amount of 3.7g of terephthalic acid (supplied by Sigma Aldrich), 3.3g of cyclohexanedimethanol (supplied by Sigma Aldrich) and 0.013g of antimony trioxide (supplied by Sigma Aldrich) were added to the reactor. The reactor was sealed and purged with nitrogen for about 20 minutes. The contents of the reactor were mixed by overhead mixing at about 150rpm using a glass stirrer. The headspace of the reactor was then evacuated to-28.9 "Hg and refilled with nitrogen for three cycles. The contents of the reactor were then gradually heated to 285 ℃ under nitrogen over a period of about 1 hour. The contents were held at 285 ℃ for an additional 90 minutes. The pressure in the vessel was then reduced by applying a vacuum to-28.8 "Hg. The reaction was continued under vacuum at 285 deg.C for about 3.5 hours. The volatiles were collected via a short path distillation column and a condenser flask cooled by dry ice. To stop the reaction, stirring and heating were stopped and the reactor was purged with nitrogen to return to atmospheric pressure. The contents were cooled overnight to ambient temperature (nominally 20-25 degrees celsius). The final mole% (relative to the total diol content) of cyclohexanedimethanol is 30%.
Differential Scanning Calorimetry (DSC) of the final product showed no crystallinity and a Tg of 79 ℃.
To evaluate foamability, samples were pressed into films and tested for foamability using the method described above. The sample expanded in volume and showed evidence of void formation, indicating successful foaming. DSC was performed on the post-foaming material and no evidence of crystallinity was detected, as there was a hot melt peak in the first heating scan of the sample.
Example 2: reaction of polyester with cyclohexanedimethanol
Virgin poly (ethylene terephthalate) (10g) supplied by Muehlstein corporation was added to a 100ml glass reactor at room temperature. Next, an amount of 2.3g cyclohexanedimethanol (supplied by Sigma Aldrich) and 0.012g antimony trioxide (supplied by Sigma Aldrich) were added to the reactor. The reactor was sealed and purged with nitrogen for about 20 minutes. The contents of the reactor were mixed by overhead mixing at about 150rpm using a glass stirrer. The headspace of the reactor was then evacuated to-28.6 "Hg and refilled with nitrogen for three cycles. The contents of the reactor were then gradually heated to 285 ℃ under nitrogen over a period of about 1 hour. The contents were held at 285 ℃ for an additional 90 minutes. The pressure in the vessel was then reduced by applying a vacuum to-28.5 "Hg. The reaction was continued under vacuum at 285 deg.C for about 3.5 hours. The volatiles were collected via a short path distillation column and a condenser flask cooled by dry ice. To stop the reaction, stirring and heating were stopped and the reactor was purged with nitrogen to return to atmospheric pressure. The contents were cooled overnight to ambient temperature (nominally 20-25 degrees celsius). The final target mole% (relative to the total diol content) of cyclohexanedimethanol is 30%.
Differential Scanning Calorimetry (DSC) of the final product showed no crystallinity and a Tg of 76 ℃.
Example 3: reaction of polyester with isosorbide and terephthalic acid
Virgin poly (ethylene terephthalate) (10g) supplied by Muehlstein corporation was added to a 100ml glass reactor at room temperature. Next, an amount of 2.85g terephthalic acid (supplied by sigma aldrich), 2.55g isosorbide (supplied by sigma aldrich) and 0.014g antimony trioxide (supplied by sigma aldrich) were added to the reactor. The reactor was sealed and purged with nitrogen for about 20 minutes. The contents of the reactor were mixed by overhead mixing at about 150rpm using a glass stirrer. The headspace of the reactor was then evacuated to-28.6 "Hg and refilled with nitrogen for three cycles. The contents of the reactor were then gradually heated to 285 ℃ under nitrogen over a period of about 1 hour. The contents were held at 285 ℃ for an additional 90 minutes. The pressure in the vessel was then reduced by applying a vacuum to-28.6 "Hg. The reaction was continued under vacuum at 285 deg.C for about 3.5 hours. The volatiles were collected via a short path distillation column and a condenser flask cooled by dry ice. To stop the reaction, stirring and heating were stopped and the reactor was purged with nitrogen to return to atmospheric pressure. The contents were cooled overnight to ambient temperature (nominally 20-25 degrees celsius). The final molar% of isosorbide (relative to the total diol content) is 25%.
DSC of the final product before any attempt to foam showed no crystallinity and Tg of 107 ℃.
Example 4: reaction of polyester with isosorbide
Virgin poly (ethylene terephthalate) (15g) supplied by Muehlstein corporation was added to a 100ml glass reactor at room temperature. Next, an amount of 2.9g isosorbide (supplied by sigma aldrich) and 0.02g antimony trioxide (supplied by sigma aldrich) was added to the reactor. The reactor was sealed and purged with nitrogen for about 20 minutes. The contents of the reactor were mixed by overhead mixing at about 150rpm using a glass stirrer. The headspace of the reactor was then evacuated to-28.8 "Hg and refilled with nitrogen for three cycles. The contents of the reactor were then gradually heated to 285 ℃ under nitrogen over a period of about 1 hour. The contents were held at 285 ℃ for an additional 90 minutes. The pressure in the vessel was then reduced by applying a vacuum to-28.7 "Hg. The reaction was continued under vacuum at 285 deg.C for about 3.5 hours. The volatiles were collected via a short path distillation column and a condenser flask cooled by dry ice. To stop the reaction, stirring and heating were stopped and the reactor was purged with nitrogen to return to atmospheric pressure. The contents were cooled overnight to ambient temperature (nominally 20 ℃ -25 ℃). The final target mole% (relative to the total diol content) of isosorbide is 25%.
DSC of the final product before any attempt to foam showed no crystallinity and Tg of 97 ℃.
Example 5: reaction of polyester with cyclobutanediol and terephthalic acid
Virgin poly (ethylene terephthalate) (6g) supplied by Muehlstein corporation was added to a 100ml glass reactor at room temperature. Next, an amount of 4.6g terephthalic acid (supplied by sigma aldrich), 5.2g cyclobutanediol (supplied by sigma aldrich) and 0.018g antimony trioxide (supplied by sigma aldrich) were added to the reactor. The reactor was sealed and purged with nitrogen for about 20 minutes. The contents of the reactor were mixed by overhead mixing at about 150rpm using a glass stirrer. The headspace of the reactor was then evacuated to-28.9 "Hg and refilled with nitrogen for three cycles. The contents of the reactor were then gradually heated to 285 ℃ under nitrogen over a period of about 1 hour. The contents were held at 285 ℃ for an additional 90 minutes. The pressure in the vessel was then reduced by applying a vacuum to-29 "Hg. The reaction was continued under vacuum at 285 deg.C for about 3.5 hours. The volatiles were collected via a short path distillation column and a condenser flask cooled by dry ice. To stop the reaction, stirring and heating were stopped and the reactor was purged with nitrogen to return to atmospheric pressure. The contents were cooled overnight to ambient temperature (nominally 20 ℃ -25 ℃). The final mole% (relative to the total glycol content) of cyclobutanediol was 50%.
The product was DSC prior to any attempted foaming, showing no crystallinity and a Tg of 107 ℃.
To evaluate foamability, samples were pressed into films and tested for foamability using the method described above. The sample showed evidence of void formation, indicating successful foaming. DSC was performed on the post-foaming material and no evidence of crystallinity was detected, as there was a hot melt peak in the first heating scan of the sample.
Example 6: reaction of recycled polyester with cyclohexanedimethanol and terephthalic acid
Recycled polyester was obtained as transparent pellets from Clean Tech recycles (dunde, MI). Recycled PET (10g) was added to a 100ml glass reactor at room temperature. Next, an amount of 3.8g terephthalic acid (supplied by sigma aldrich), 3.4g cyclohexanedimethanol (supplied by sigma aldrich) and 0.013g antimony trioxide (supplied by sigma aldrich) were added to the reactor. The reactor was sealed and purged with nitrogen for about 20 minutes. The contents of the reactor were mixed by overhead mixing at about 150rpm using a glass stirrer. The headspace of the reactor was then evacuated to-28.7 "Hg and refilled with nitrogen for three cycles. The contents of the reactor were then gradually heated to 285 ℃ under nitrogen over a period of about 1 hour. The contents were held at 285 ℃ for an additional 90 minutes. The pressure in the vessel was then reduced by applying a vacuum to-28.8 "Hg. The reaction was continued at 285 degrees celsius for about 3.5 hours under vacuum. The volatiles were collected via a short path distillation column and a condenser flask cooled by dry ice. To stop the reaction, stirring and heating were stopped and the reactor was purged with nitrogen to return to atmospheric pressure. The contents were cooled overnight to ambient temperature (nominally 20-25 degrees celsius). The final mole% (relative to the total diol content) of cyclohexanedimethanol is 30%.
Differential Scanning Calorimetry (DSC) of the final product showed no crystallinity and a Tg of 79 ℃.
To evaluate foamability, samples were pressed into films and tested for foamability using the method described above. The sample showed evidence of void formation, indicating successful foaming. DSC was performed on the post-foaming material and no evidence of crystallinity was detected, as there was a hot melt peak in the first heating scan of the sample.
Example 7: reaction of recycled polyester with isosorbide and terephthalic acidRecycled polyester was obtained as transparent pellets from Clean Tech recycles (dunde, MI). Recycled PET (10g) was added to a 100ml glass reactor at room temperature. Next, quantities of 2.87g terephthalic acid (supplied by Sigma Aldrich), 2.57g isosorbide (supplied by Sigma Aldrich) and 0.0 g16g of antimony trioxide (supplied by sigma aldrich) was added to the reactor. The reactor was sealed and purged with nitrogen for about 20 minutes. The contents of the reactor were mixed by overhead mixing at about 150rpm using a glass stirrer. The headspace of the reactor was then evacuated to-28.8 "Hg and refilled with nitrogen for three cycles. The contents of the reactor were then gradually heated to 285 ℃ under nitrogen over a period of about 1 hour. The contents were held at 285 ℃ for an additional 90 minutes. The pressure in the vessel was then reduced by applying a vacuum to-28.9 "Hg. The reaction was continued under vacuum for about 3.5 hours. The volatiles were collected via a short path distillation column and a condenser flask cooled by dry ice. To stop the reaction, stirring and heating were stopped and the reactor was purged with nitrogen to return to atmospheric pressure. The contents were cooled overnight to ambient temperature (nominally 20-25 degrees celsius). The final molar% of isosorbide (relative to the total diol content) is 25%.
DSC was run on the final product before any attempt to foam, which showed no crystallinity present and Tg of 106 ℃.
To evaluate foamability, samples were pressed into films and tested for foamability using the method described above. The sample showed evidence of void formation, indicating successful foaming. DSC was performed on the post-foaming material and no evidence of crystallinity was detected, as there was a hot melt peak in the first heating scan of the sample.
Example 8: polyester to Unoxol (1: 1 ratio of 1,3 and 1,4 cyclohexanedimethanol isomers) Blend) and isophthalic acid
Virgin poly (ethylene terephthalate) (9.7g) provided by Muehlstein corporation was added to a 100ml glass reactor at room temperature. Next, an amount of 2.8g terephthalic acid (supplied by sigma aldrich), 2.5g Unoxol (a mixture of cyclohexane dimethanol isomers supplied by Dow Chemical) and 0.013g antimony trioxide (supplied by sigma aldrich) were added to the reactor. The reactor was sealed and purged with nitrogen for about 20 minutes. The contents of the reactor were mixed by overhead mixing at about 160rpm using a glass stirrer. The headspace of the reactor was then evacuated to 0mbar and refilled with nitrogen for three cycles. The contents of the reactor were then gradually heated to 285 ℃ under nitrogen over a period of about 1 hour. The contents were held at 285 ℃ for an additional 45 minutes. The pressure in the vessel was then reduced by applying a vacuum to 0 mbar. The reaction was continued at 285 degrees celsius for about 3.5 hours under vacuum. The volatiles were collected via a short path distillation column and a condenser flask cooled by dry ice. To stop the reaction, stirring and heating were stopped and the reactor was purged with nitrogen to return to atmospheric pressure. The contents were cooled overnight to ambient temperature (nominally 20-25 degrees celsius). The final mole% (relative to the total diol content) of cyclohexanedimethanol is 25%. The final molar% of isophthalic acid (relative to the total diacid content) was 25%.
DSC of the final product before any attempt to foam showed no crystallinity and Tg of 72 ℃.
To evaluate foamability, samples were pressed into films and tested for foamability using the method described above. The sample showed evidence of void formation, indicating successful foaming. The crystallinity of the sample after foaming was measured using DSC. The first heat sweep is used to determine if any crystallinity is formed. No evidence of crystallization was detected (temperature range 125 ℃ -225 ℃).
The molecular weights of the foamable resins are summarized in table 1.
TABLE 1
Example numbering
Mn
Mw
Mz
Mz+1
1
45
24027
40810
56632
2
251
27507
46927
67766
3
9046
41348
96452
573293
4
9131
25250
40850
57446
5
602
11405
20650
28929
6
7438
25062
95168
3287516
7
7202
35446
259553
3400509
Mn is the number average molecular weight, Mw is the weight average molecular weight, and Mz is the Z average molecular weight. Mz +1 is the average Z + 1.