CN111875728B - Carbodiimide polymer, method for producing the same, and polymer material containing the same - Google Patents
Carbodiimide polymer, method for producing the same, and polymer material containing the same Download PDFInfo
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- CN111875728B CN111875728B CN202010805965.3A CN202010805965A CN111875728B CN 111875728 B CN111875728 B CN 111875728B CN 202010805965 A CN202010805965 A CN 202010805965A CN 111875728 B CN111875728 B CN 111875728B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F112/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F112/34—Monomers containing two or more unsaturated aliphatic radicals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
Abstract
The invention discloses a carbodiimide polymer, a preparation method thereof and a polymer material containing the same, wherein the structural formula of the carbodiimide polymer is shown as a formula I, and the preparation method comprises the following steps: bis [ 3-isopropenyl-dimethylbenzyl group]Adding an initiator into a mixture of carbodiimide and an organic solvent, and carrying out addition polymerization for 2-5 hours at the temperature of 30-60 ℃. The carbodiimide-based polymer-containing polymer material of the invention includes a carbodiimide-based polymer and an ester-based polymer-containing material. The carbodiimide polymer disclosed by the invention has excellent thermal stability, is not easy to decompose in the processing process, has a high softening point, can realize simple blending with plastic particles, and reduces the processing difficulty; the material has good compatibility with materials, and is not easy to migrate in the using process; the preparation method can obtain the polymer with large molecular weight under relatively mild conditions; the polymer material containing the epoxy resin has high ageing resistance and strong mechanical property.
Description
Technical Field
The invention relates to a carbodiimide polymer, a preparation method thereof and a polymer material containing the carbodiimide polymer.
Background
Carbodiimide compounds have been proven to be excellent as hydrolysis stabilizers for a range of materials such as thermoplastics, polyols, polyurethanes, and the like. The most obvious characteristic of the materials is that the molecular structure of the materials contains ester bonds, and the existence of the ester bonds causes the materials to be easy to break the ester bonds under the moist or higher temperature to form terminal carboxyl. The terminal carboxyl further catalyzes the hydrolysis to accelerate the breakage of molecular chains, so that the service performance of the material is greatly reduced. The existence of the carbodiimide compound can eliminate residual acid and terminal carboxyl in the polymer and inhibit the occurrence of hydrolysis, thereby greatly prolonging the service life of the material and improving the service performance of the polymer material to a certain extent.
At present, the common carbodiimide compounds are largely divided into monomeric carbodiimide and polymeric carbodiimide. The common monomeric and polymeric carbodiimides are mainly synthesized by monomeric isocyanate or diisocyanate under the catalytic action of a cyclophosphene oxide, phosphlidine or cyclophosphene sulfide catalyst. Two representative carbodiimide compounds, such as those disclosed in CN 105209585 and CN 107001245A, are produced using heterocyclic phosphorus compound catalysts. CN 106458865A relates to a new synthesis method of bis [ 3-isopropenyl-dimethylbenzyl ] carbodiimide, adopts novel alkaline cesium salt, greatly improves the production yield of bis [ 3-isopropenyl-dimethylbenzyl ] carbodiimide, and provides possibility for industrial production of bis [ 3-isopropenyl-dimethylbenzyl ] carbodiimide. However, bis [ 3-isopropenyl-dimethylbenzyl ] carbodiimide is a monomeric carbodiimide, has poor thermal stability, is easily degraded and loses efficacy in the processing process, particularly when used in occasions with higher processing temperature requirements such as PET, PA and PC, and can release a large amount of small molecular substances to pollute the environment due to degradation in the processing process. The carbodiimide compound added to the polymer is inferior in compatibility and is likely to migrate compared with a polymeric carbodiimide compound.
Disclosure of Invention
The invention provides a carbodiimide polymer, a preparation method thereof and a polymer material containing the carbodiimide polymer, aiming at solving the defects of poor thermal stability, poor compatibility with polymers, low ageing resistance and low mechanical property of the carbodiimide hydrolysis-resistant stabilizer in the prior art.
One of the purposes of the invention is to provide a carbodiimide polymer, wherein the carbodiimide polymer is poly-bis [ 3-isopropenyl-dimethylbenzyl ] carbodiimide, and the structural formula of the carbodiimide polymer is shown as a formula I:
wherein the carbodiimide polymer has a number average molecular weight of 5000 to 30000g/mol and a degree of polymerization of 14 to 84.
Preferably, the number average molecular weight is 10000 to 20000g/mol, and the polymerization degree is 28 to 56.
In the invention, the mobility and compatibility of the polymer in the base material are influenced by the number average molecular weight, and if the molecular weight is too small, the thermal degradation performance of the polymer is reduced, and the polymer is easy to migrate and separate out from the base material; if the molecular weight is too large, compatibility with the base polymer may be deteriorated.
In the invention, the carbodiimide polymer is used as an ester hydrolysis-resistant stabilizer, has excellent thermal stability, is not easy to decompose in the processing process, has a high softening point, has a glass transition temperature of 150-160 ℃, can realize simple blending with plastic particles, and reduces the processing difficulty. Generally, the softening point of the carbodiimide-based polymer is 145 to 160 ℃ and the softening point is preferably 152 to 155 ℃.
In the invention, the carbodiimide polymer is used as an anti-hydrolysis stabilizer, belongs to a polymeric anti-hydrolysis stabilizer, can have very good compatibility with materials, and is not easy to migrate in the using process.
The second purpose of the invention is to provide a preparation method of a carbodiimide polymer, which comprises the steps of adding an initiator into a mixture of bis [ 3-isopropenyl-dimethylbenzyl ] carbodiimide and an organic solvent, and carrying out addition polymerization for 2-5 hours at the temperature of 30-60 ℃ to obtain the carbodiimide polymer;
the initiator comprises:
a first component: halide or hydroxy acid salts of transition metals;
a second component: alR 3 LiR or ZnR 2 Wherein R is alkyl or cycloalkyl;
the dosage of the initiator is 50-1000 ppm; wherein the molar ratio of the first component to the second component is 1:10 to 1:50; the amount of the initiator is used for guiding the mass concentration ratio of the initiator relative to the bis [ 3-isopropenyl-dimethylbenzyl ] carbodiimide.
In the present invention, the reaction product is a generally powdery substance.
Preferably, the initiator is used in an amount of 200 to 600ppm, for example 350ppm or 400ppm.
Preferably, the molar ratio of the first component to the second component is 1:15 to 1:25, as shown in 1:15 or 1:20.
preferably, the transition metal is Co, ni, ru, rh, mo or Fe.
Preferably, the initiator comprises a hydroxy acid salt of Fe and AlR 3 (ii) a Or molybdenum compound and AlR 3 (ii) a Such as iron acetylacetonate and triisobutylaluminum, moCl 5 And Al (i-Bu) 3 。
In the present invention, the addition polymerization is carried out as is conventional in the art, generally under the protection of an inert gas or nitrogen.
In the present invention, the organic solvent is a solvent conventionally used in the art, and may be one or more of carbon sulfide, a haloalkane-type solvent and an aromatic-type solvent, and is preferably one or more of dichloroethane, chlorobenzene, benzene and toluene.
Preferably, the mass concentration of the bis [ 3-isopropenyl-dimethylbenzyl ] carbodiimide in the organic solvent is 200 g/L-400 g/L.
Preferably, the temperature is 40 ℃ or 50 ℃.
Preferably, the time of the addition polymerization is 1h, 3h, 4h or 6h.
In the present invention, the polyaddition reaction is followed by washing with a washing solvent as is customary in the art to give the final product. Wherein the washing solvent is a washing solvent which is conventional in the field, and methanol or ethanol is preferred.
It is a further object of the present invention to provide a carbodiimide-based polymer produced by the above-mentioned method for producing a carbodiimide-based polymer.
A fourth object of the present invention is to provide a polymer material containing the above-mentioned carbodiimide-based polymer, which comprises the above-mentioned carbodiimide-based polymer and a material containing an ester-based polymer, wherein the mass concentration of the above-mentioned carbodiimide-based polymer is 0.1 to 15%; preferably 0.5 to 5 percent; more preferably 0.5% to 2%; further preferably 1%.
In the present invention, the ester polymer-containing material is conventional in the art, and includes an ester polymer or an ester polymer-containing composition.
In the present invention, the ester polymer is conventional in the art, and is preferably one or more of polyurethane, polyester polyol, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), polylactic acid (PLA) derivatives, polyhydroxyalkanoate (PHA) and polybutylene succinate (PBS), modified Polyester of Cyclohexanediol and Terephthalic Acid (PCTA), thermoplastic polyester elastomer (TPEE), ethylene-vinyl acetate copolymer (EVA), and polybutylene terephthalate-adipate (PBAT); more preferably polyethylene terephthalate (PET); more preferably, polyethylene terephthalate (PET) having an intrinsic viscosity of 0.60 to 0.95dL/g, for example, polyethylene terephthalate (PET) having an intrinsic viscosity of 0.74dL/g is used.
Wherein, the polyester polyol is conventional in the field, and is preferably one or more of adipic acid polyester diol, polycaprolactone polyol and polycarbonate diol.
In the present invention, the compositions containing ester polymers are conventional in the art, such as blends containing ester polymers, oil formulations for the lubricant industry or polyurethane materials.
Wherein the ester polymer-containing blend is conventional in the art, preferably a polyamide/polyethylene terephthalate (PA/PET) blend or a polyhydroxyalkanoate/polylactic acid (PHA/PLA) blend.
Among these, the oil formulations used in the lubricant industry are conventional in the art and, in general, will contain triglycerides, synthetic carboxylate phosphotriesters and olefin-dicarboxylic acid polymers in the base of a range of base oils and lubricating oils.
Wherein, the polyurethane material is conventional in the field, and is preferably polyurethane elastomer, polyurethane adhesive, polyurethane foam or polyurethane coating;
wherein the polyurethane elastomer is conventional in the art, preferably a cast polyurethane elastomer (CPU) or a thermoplastic polyurethane elastomer (TPU);
the polyurethane foam is a high molecular polymer which is prepared by mixing isocyanate and polyester serving as main raw materials under the action of various auxiliary agents such as a foaming agent, a catalyst, a flame retardant and the like through special equipment and performing high-pressure spraying and on-site foaming according to the conventional method in the field;
wherein said polyurethane coating is conventional in the art and refers to a coating comprising polyurethane.
On the basis of the common knowledge in the field, the above preferred conditions can be combined randomly to obtain the preferred embodiments of the invention.
The reagents and starting materials used in the present invention are commercially available.
The positive progress effects of the invention are as follows:
1. the carbodiimide polymer disclosed by the invention has excellent thermal stability, is not easy to decompose in the processing process, has a high softening point, can realize simple blending with plastic particles, and reduces the processing difficulty.
2. The carbodiimide polymer has good compatibility with materials, and is not easy to migrate in the using process.
3. The method for producing a carbodiimide-based polymer of the present invention can produce a polymer having a large molecular weight under relatively mild conditions.
4. The polymer material containing the carbodiimide polymer has high ageing resistance and strong mechanical property.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the invention thereto. Experimental procedures without specifying specific conditions in the following examples were selected in accordance with conventional procedures and conditions, or in accordance with commercial instructions.
In the following examples, the softening point is related to the molecular weight, and the higher the softening point, the higher the molecular weight.
Polyethylene terephthalate (PET) used in the following examples was purchased from China certified chemical fibers, inc. under the type FG720 and had an intrinsic viscosity of 0.74dL/g.
Example 1
100g of bis [ 3-isopropenyl-dimethylbenzyl ] carbodiimide and 500ml of toluene are added into a 1000ml glass reaction bottle, and the mixture is sequentially added with a molar ratio of 1:15 of iron acetylacetonate and triisobutylaluminum initiator (35 mg in total (350 ppm)) were reacted in a thermostatic water bath at 40 ℃ for 3 hours. After the reaction is finished, adding a small amount of ethanol into the reaction system for washing to obtain a white powdery solid polymer with a softening point of 152 ℃.
Example 2
2000g of bis [ 3-isopropenyl-dimethylbenzyl]Carbodiimide and 5000ml dichloroethane are added into a 10L glass reaction kettle, and under the protection of nitrogen, the materials are sequentially added according to the mol ratio of 1:20 MoCl 5 And Al (i-Bu) 3 A total of 800mg (400 ppm) of initiator were reacted in a thermostatic water bath at 50 ℃ for 4 hours. After the reaction, a small amount of methanol was added to the reaction system to wash the mixture, thereby obtaining a white powdery solid polymer having a softening point of 155 ℃.
Example 3
200g of bis [ 3-isopropenyl-dimethylbenzyl ] carbodiimide and 1000ml of toluene are added into a 1000ml glass reaction bottle, and the mixture is sequentially added with a molar ratio of 1:15 of iron acetylacetonate and triisobutylaluminum initiator (10 mg in total (50 ppm)) were reacted in a thermostatic water bath at 40 ℃ for 1 hour. After the reaction is finished, adding a small amount of ethanol into the reaction system for washing to obtain a white powdery solid polymer, wherein the softening point is 145 ℃.
Comparative example 1
Bis [ 3-isopropenyl-dimethylbenzyl ] carbodiimide was prepared by the method of example 1 of WO-A2005/111136 (page 7, line 26 to page 8, line 2 of the description).
Comparative example 2
200g of bis [ 3-isopropenyl-dimethylbenzyl ] carbodiimide and 1000ml of toluene are added into a 1000ml glass reaction bottle, and the mixture is sequentially added with a molar ratio of 1:15 of iron acetylacetonate and triisobutylaluminum initiator (total amount: 220mg, 1100 ppm) were reacted in a thermostatic water bath at 50 ℃ for 6 hours. After the reaction is finished, a small amount of ethanol is added into the reaction system for washing to obtain a white powdery solid polymer with a softening point of 161 ℃.
Effect example 1
In order to evaluate the application performance of the carbodiimide-based polymer as the hydrolysis resistance stabilizer in polyethylene terephthalate (PET) in the present invention, the carbodiimide-based compound synthesized in examples 1 and 2 and comparative example 1 was added to polyethylene terephthalate (PET) at a ratio of 1.0%, and dumbbell-shaped tensile bars were prepared by granulation and injection molding, and the bars were tested in an aging oven under a saturated vapor pressure condition of 121 ℃, and then the mechanical properties of each bar were tested. The test results of the tensile strength test of the sample strips with different aging times by using a universal tensile machine are shown in the attached table 1.
Table 1: PET sample strip added with different types of carbodiimide compounds with the same mass fraction and 121 ℃ saturated vapor pressure aging mechanical strength change
As shown in Table 1, the aging resistance of the PET sample strips obtained from the carbodiimide-based polymers of examples 1 and 2 is superior to that of comparative example 1, i.e., the polymer material containing the carbodiimide-based polymer of the present invention has high aging resistance.
Effect example 2
In order to evaluate the compatibility of the carbodiimide-based polymer of the invention as a stabilizer against hydrolysis in polyethylene terephthalate (PET), the carbodiimide-based compound synthesized in examples 1, 3, 4 and comparative example 1 was added to polyethylene terephthalate (PET) at a ratio of 1.0%, pelletized, injection-molded to prepare dumbbell-shaped tensile bars, and then each bar was tested for mechanical properties. The tensile strength of the sample strip is tested by using a universal tensile machine, the compatibility of the material can be indirectly reflected by the tensile strength, and the test result is shown in table 2.
Table 2: PET sample strip mechanical strength added with same mass fraction different types of carbodiimide compounds
| Tensile Strength (MPa) | |
| Blank PET | 57.23 |
| Comparative example 1 | 68.45 |
| Example 1 | 71.24 |
| Example 3 | 68.56 |
| Comparative example 2 | 56.45 |
As shown in Table 2, the mechanical strength of the PET sample strips produced from the carbodiimide-based polymers of examples 1 and 3 is higher than that of the blank PET and comparative example 2, i.e., the mechanical properties of the polymer material containing the carbodiimide-based polymer of the invention are improved. When the initiator is used in an amount of 200-600 ppm, for example, 350ppm in example 1, the polymer material containing the initiator has better mechanical properties and tensile strength of 71.24MPa.
Claims (20)
1. A method for producing a carbodiimide-based polymer, characterized by comprising the steps of: adding an initiator into a mixture of bis [ 3-isopropenyl-dimethylbenzyl ] carbodiimide and an organic solvent, and carrying out addition polymerization for 2-5 hours at the temperature of 30-60 ℃ to obtain the product;
wherein the initiator comprises:
a first component: a halide or hydroxy acid salt of a transition metal;
a second component: alR 3 LiR or ZnR 2 Wherein R is alkyl or cycloalkyl;
the dosage of the initiator is 200-1000 ppm; wherein the molar ratio of the first component to the second component is 1:10 to 1:50; the amount of the initiator is used for guiding the mass concentration ratio of the initiator relative to the bis [ 3-isopropenyl-dimethylbenzyl ] carbodiimide.
2. The method for producing the carbodiimide-based polymer according to claim 1, wherein the amount of the initiator is 200 to 600ppm;
and/or the molar ratio of the first component to the second component is 1:15 to 1:25.
3. the method for producing the carbodiimide-based polymer according to claim 2, wherein the amount of the initiator is 350ppm or 400ppm;
and/or the molar ratio of the first component to the second component is 1.
4. The method for producing the carbodiimide-based polymer according to claim 1, wherein the transition metal is Co, ni, ru, rh, mo or Fe;
and/or, the initiator comprises hydroxy acid of FeSalts and AlR 3 Or a molybdenum compound and AlR 3 。
5. The method of claim 4, wherein the initiator comprises ferric acetylacetonate and triisobutylaluminum, or MoCl 5 And Al (i-Bu) 3 。
6. The method of preparing a carbodiimide-based polymer of 1~5 wherein said organic solvent is one or more of a carbon sulfide, a haloalkane solvent and an aromatic solvent;
and/or the mass concentration of the bis [ 3-isopropenyl-dimethylbenzyl ] carbodiimide in the organic solvent is 200-400 g/L;
and/or the addition polymerization is carried out under the protection of inert gas or nitrogen;
and/or, further comprising washing after said polyaddition reaction;
and/or, the temperature is 40 ℃ or 50 ℃;
and/or the time of the polyaddition reaction is 3h or 4h.
7. The process for producing the carbodiimide-based polymer according to claim 6, wherein the organic solvent is one or more of dichloroethane, chlorobenzene, benzene, and toluene;
and/or the washing solvent for washing is methanol or ethanol.
8. The method of claim 1~5, wherein said carbodiimide-based polymer is poly [ 3-isopropenyl-dimethylbenzyl ] carbodiimide, said carbodiimide-based polymer has a number average molecular weight of 5000 to 30000g/mol and a degree of polymerization of 14 to 84.
9. The method for producing the carbodiimide-based polymer according to claim 8, wherein the carbodiimide-based polymer has a number average molecular weight of 10000 to 20000g/mol and a degree of polymerization of 28 to 56; the carbodiimide polymer is a carbodiimide polymer with a softening point of 145-160 ℃.
10. The method for producing the carbodiimide-based polymer according to claim 9, wherein the carbodiimide-based polymer is a carbodiimide-based polymer having a softening point of from 152 ℃ to 155 ℃.
11. A carbodiimide compound polymer produced by the method for producing a carbodiimide compound polymer according to any one of claims 1 to 10.
12. A carbodiimide polymer-containing polymer material, which comprises the carbodiimide polymer according to claim 11 and an ester polymer-containing material, wherein the mass concentration of the carbodiimide polymer is 0.1 to 15%.
13. The carbodiimide-based polymer-containing polymeric material of claim 12, wherein the mass concentration of the carbodiimide-based polymer is 0.5% to 5%.
14. The carbodiimide-based polymer-containing polymeric material of claim 13, wherein the mass concentration of the carbodiimide-based polymer is 0.5% to 2%.
15. The carbodiimide-based-polymer-containing polymeric material of claim 14, wherein the carbodiimide-based polymer is present at a mass concentration of 1%.
16. The carbodiimide-based polymer-containing polymeric material of claim 12, wherein the ester-based polymer-containing material comprises an ester-based polymer or an ester-based polymer-containing composition.
17. The carbodiimide-based polymer-containing polymeric material of claim 16, wherein the ester-based polymer is one or more of polyurethane, polyester polyol, polyethylene terephthalate, polybutylene terephthalate, polypropylene terephthalate, polylactic acid derivatives, polyhydroxyalkanoates, and polybutylene succinate, modified polyesters of cyclohexanediol and terephthalic acid, thermoplastic polyester elastomers, ethylene-vinyl acetate copolymers, and polybutylene terephthalate-adipate; wherein the polyester polyol is one or more of adipic acid polyester diol, polycaprolactone polyol and polycarbonate diol;
and/or the composition containing the ester polymer is an oil preparation or a polyurethane material for the lubricant industry, wherein the oil preparation for the lubricant industry is an oil preparation containing triglyceride, synthetic carboxylic ester phosphoric triester and olefin-dicarboxylic acid polymer in the base components of base oil and lubricating oil.
18. The carbodiimide-based polymer-containing polymeric material of claim 17, wherein the ester polymer is polyethylene terephthalate;
and/or the polyurethane material is a polyurethane elastomer, a polyurethane adhesive, a polyurethane foam or a polyurethane coating; wherein the polyurethane elastomer is a cast polyurethane elastomer or a thermoplastic polyurethane elastomer.
19. The carbodiimide-based polymer material of claim 18, wherein the ester polymer is polyethylene terephthalate having an intrinsic viscosity of 0.60 to 0.95 dL/g.
20. The carbodiimide-based polymer-containing polymeric material of claim 19, wherein the ester polymer is polyethylene terephthalate having an intrinsic viscosity of 0.74dL/g.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1954027A (en) * | 2004-05-13 | 2007-04-25 | 巴斯福股份公司 | Polyurethane containing carbodiimides |
| WO2018207951A1 (en) * | 2017-05-10 | 2018-11-15 | Japan Polypropylene Corporation | Method for producing propylene-ethylene-1-butene terpolymer |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1954027A (en) * | 2004-05-13 | 2007-04-25 | 巴斯福股份公司 | Polyurethane containing carbodiimides |
| WO2018207951A1 (en) * | 2017-05-10 | 2018-11-15 | Japan Polypropylene Corporation | Method for producing propylene-ethylene-1-butene terpolymer |
Non-Patent Citations (1)
| Title |
|---|
| Fe(acac)_3-Al(i-Bu)_3催化甲基丙烯酸丁酯聚合;胡富陶等;《宁波大学学报(理工版)》;20020630(第02期);第1-2节，表1，表2 * |
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