CN109749403B - Polyureide elastomer and preparation method and application thereof - Google Patents
Polyureide elastomer and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a polyimide-based urea elastomer and a preparation method and application thereof. The preparation method comprises the following steps: uniformly mixing polycarbodiimide, polymer at least containing two acidic functional groups, and optional chain extender, plasticizer, catalyst and solvent; then, curing is performed to obtain the polyurethaneurea elastomer. The invention can effectively solve the problem that the polyurethane material is sensitive to water vapor in the preparation process, application and construction process; the polyamide-urea elastomer does not contain free isocyanate, so that the problem of harm of the free isocyanate can be solved.
Description
Technical Field
The invention belongs to the technical field of elastomer materials, and particularly relates to a polyamide-urea elastomer and a preparation method and application thereof.
Background
Polyurethane materials were first synthesized in 1937 by ottoayer for over 80 years. Polyurethane products (elastomers and foams) entered the market at the end of the 40's 20 th century and, by virtue of their excellent properties, rapidly held their place in the market. Polyurethane plastics have been used as an important member of plastic families, and have been widely applied to various engineering fields, including the fields of chemical industry, electronics, architecture, textile, automobiles, medical treatment, national defense, aerospace and the like. Compared with other high polymer materials, the performance of the polyurethane material can be adjusted to a great extent by selecting different raw materials, catalysts and auxiliaries or different molding processing and post-treatment methods. The principle is that in the polymerization process of the isocyanate compound and the polyol component, the formed hard segment and soft segment have different compatibility, and further a hard segment area and a soft segment area are formed, so that the excellent performances of the polyurethane material such as elasticity, strength, abrasion resistance, hardness and the like are integrated. At present, polyurethane is the only synthetic polymer material with great application value in seven fields of paint, foam, plastic, rubber, fiber, adhesive and functional polymer, and has become a special organic synthetic material with the most varieties, the most extensive use and the fastest development at present.
Polyurethanes, also known as polyurethanes, are obtained primarily by the addition reaction of isocyanate groups (-NCO) and hydroxyl groups (-OH), i.e., the transfer of active hydrogen atoms in hydroxyl groups to isocyanate groups. Because isocyanate groups have high reactivity and react with hydroxyl groups and simultaneously react with water to generate side reaction and release carbon dioxide gas, when polyurethane is used as coating, adhesive and elastomer, the polyurethane often needs to avoid the reaction of-NCO and water by some means so as to avoid the production of bubbles and reduce the product performance, thereby increasing the complexity of the production process and the construction process. The reaction is shown as the following formula 1; in the production process of many polyurethane products, such as polyurethane waterproof coatings, sealing adhesives and other products containing inorganic fillers, the water content of raw materials such as powder, polyol, solvents, auxiliaries and the like needs to be strictly controlled, and the process is relatively complex if measures such as high-purity nitrogen protection, powder drying, vacuum dehydration and the like are adopted; meanwhile, the field construction is seriously influenced by the environment and has high sensitivity to the temperature and humidity of the environment, and a large amount of bubbles can be generated in a coating film when the environment is serious, so that the service performance of a product is influenced. In order to reduce the risk of the construction process, various latent curing agents are developed, and the latent curing agents absorb water vapor in the environment, are converted into alcoholic hydroxyl groups or amino groups, and are further crosslinked with isocyanate. The reaction is a competitive reaction of isocyanate and water, and the influence of the temperature and the humidity of the construction process environment can be reduced to a certain extent. However, the isocyanate activity is high, and the application of the latent curing agent cannot completely eliminate the reaction of-NCO and water.
Reaction of isocyanate group with hydroxyl group and Water
Furthermore, isocyanate monomers tend to be highly toxic and unhealthy to inhale into humans, especially Toluene Diisocyanate (TDI) and Hexamethylene Diisocyanate (HDI) having high vapor pressures. It is necessary to extract free diisocyanate and to enhance ventilation during polyurethane coating applications. In order to solve the residual hazard of toxic monomers in the production process of polyurethane materials, a great deal of research is focused on the synthesis of non-isocyanate polyurethane, and the main completion approaches are as follows: cyclic carbonates (shown as formula 3), ester exchange methods (shown as formula 2), etc. Although the residual problem of toxic monomers can be reduced, the complicated operation process thereof causes a great increase in production cost, and is difficult to be applied to the market on a large scale.
Formula 2 preparation of polyurethane by transesterification
Preparation of polyurethanes by the carbonate Process of formula 3 Ring
Disclosure of Invention
The invention aims to solve the problems that isocyanate groups are sensitive to water vapor, free isocyanate monomer residues are high in toxicity and the like in the preparation process of a polyurethane elastomer, and provides a polyamide urea elastomer and a preparation method thereof. The polycarbodiimide is mainly used as a curing agent, and the polymer at least containing two acidic functional groups is used as a matching component to prepare the polyimide-based urea elastomer through addition reaction.
In order to achieve the above object, a first aspect of the present invention provides a method for producing a polyureide elastomer, comprising: uniformly mixing polycarbodiimide, polymer at least containing two acidic functional groups, and optional chain extender, plasticizer, catalyst and solvent; then, curing is performed to obtain the polyurethaneurea elastomer.
The second aspect of the present invention provides a polyurethaneurea elastomer prepared by the above-described preparation method.
The third aspect of the present invention provides the use of the above-mentioned polyureide elastomer in waterproof coatings, sealants, adhesives, chemical grouting reinforcement materials and waterproof rolls.
The technical scheme of the invention has the following beneficial effects:
(1) the invention can effectively solve the problem that the polyurethane material is sensitive to water vapor in the preparation process, application and construction process; the polyamide-urea elastomer does not contain free isocyanate, so that the problem of harm of the free isocyanate can be solved.
(2) According to the invention, polycarbodiimide is used as a curing agent, and complex processes such as high-temperature dehydration and the like are not needed in the preparation of the polyimide-based urea elastomer, so that the production time can be effectively shortened and the energy consumption can be reduced.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
Preferred embodiments of the present invention will be described in more detail below. While the following describes preferred embodiments of the present invention, it should be understood that the present invention may be embodied in various forms and should not be limited by the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.
A first aspect of the present invention provides a method for producing a polyureide elastomer, comprising: uniformly mixing polycarbodiimide, polymer at least containing two acidic functional groups, and optional chain extender, plasticizer, catalyst and solvent; then, curing is performed to obtain the polyurethaneurea elastomer.
Polyureide is a polymer consisting of acylurea linkages. Which is obtained by reacting carbodiimide groups with carboxyl groups. The invention adopts isocyanate and derivatives thereof as a polycarbodiimide reactant source, removes carbon dioxide in the presence of a catalyst, converts NCO into NCN, and further carries out crosslinking or chain extension with a polymer/chain extender containing at least two acidic functional groups. The generated acyl urea bond has similar structure with carbamate bond and amido bond, has strong polarity and is easy to form strong hydrogen bond. The acyl urea group characteristics determine that the product of the polyamide urea has the comprehensive characteristics of polyurethane and polyamide, so that the polyamide urea has good mechanical properties, corrosion resistance, solvent resistance and the like. The molecular chain structure of the polycarbodiimide curing agent is similar to that of an isocyanate curing agent (the polycarbodiimide used in the invention is derived from polyurethane curing agent isocyanate), but the molecular chain does not contain NCO groups, so that the polycarbodiimide curing agent is not sensitive to water vapor, and other reactants are not sensitive to water vapor.
According to the present invention, preferably, the polycarbodiimide is used in an amount of 8 to 99 parts, the polymer having at least two acidic functional groups is used in an amount of 1 to 92 parts, the chain extender is used in an amount of 0 to 10 parts, the plasticizer is used in an amount of 0 to 30 parts, the catalyst is used in an amount of 0 to 0.5 parts, and the solvent is used in an amount of 0 to 30 parts by mass.
According to the present invention, it is preferable that the plasticizer is used in an amount of 5 to 30 parts and the solvent is used in an amount of 5 to 30 parts.
According to the present invention, preferably, the polycarbodiimide is derived from at least one of an isocyanate, an isocyanate oligomer, an adduct of an isocyanate with a polyol, and an adduct of an isocyanate with a polyamine;
the isocyanate is aliphatic isocyanate and/or aromatic isocyanate;
the aliphatic isocyanate is preferably at least one selected from the group consisting of isophorone diisocyanate, dicyclohexylmethane diisocyanate, trimethylhexamethylene diisocyanate, and hexamethylene diisocyanate;
the aromatic isocyanate is preferably at least one selected from the group consisting of toluene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate and tetramethylxylylene diisocyanate
Wherein the polycarbodiimide is preferably derived from toluene diisocyanate and/or diphenylmethane diisocyanate;
the weight average molecular weight of the polycarbodiimide is preferably 500-3000; more preferably 500-.
In the present invention, the polycarbodiimide has a functionality of 2 or more.
In the invention, the preparation method of the polycarbodiimide is a conventional preparation method in the field; polycarbodiimides may be obtained by the home-made or commercially available process.
In the present invention, the isocyanate oligomer is preferably an isocyanate dimer and/or trimer.
According to the present invention, preferably, the acidic functional group of the polymer having at least two acidic functional groups is selected from at least one of a carboxylic acid group, a carbonic acid group, a sulfonic acid group, a thiol group, a phenol group, a phosphoric acid group, and a sulfinic acid group;
the polymer containing at least two acidic functional groups is preferably at least one of unsaturated fatty acid polymer, polyester containing at least two acidic functional groups and acrylic polymer, and is further preferably at least one of dimer fatty acid, trimer fatty acid and carboxyl acrylic resin;
the unsaturated fatty acid polymer is preferably C10-C50Unsaturated fatty acid polymers of (a); more preferably C18And/or C16Unsaturated fatty acid polymer of (2)；
The weight average molecular weight of the polymer having at least two acidic functional groups is preferably 100-.
According to the present invention, preferably, the chain extender is a chain extender containing an acidic functional group and/or a chain extender containing an acid anhydride; preference is given to methyltetrahydrophthalic anhydride.
According to the present invention, preferably, the catalyst is an organic metal catalyst, preferably at least one of an organic zinc catalyst, an organic bismuth catalyst and an organic tin catalyst, and further preferably dibutyltin dilaurate; the dibutyltin dilaurate is preferably T-12 of air chemical products Co.
The plasticizer is preferably at least one selected from chlorinated paraffin, dioctyl phthalate, dibutyl phthalate, diisononyl phthalate, citrate plasticizers, vegetable oil ester plasticizers and polyether polyols; preferably diisononyl phthalate;
the plasticizer has good compatibility with the polyimide elastomer, and the plasticizer does not migrate in long-term use due to the good compatibility of the plasticizer and the polyimide elastomer, so that the stability and the cooperativity of the plasticizer are obvious.
The solvent is preferably an organic solvent, and is further preferably at least one selected from aromatic oil, toluene, xylene, ethyl acetate, butyl acetate, N-Dimethylformamide (DMF) and dimethyl sulfoxide (DMSO); the aromatic oil is preferably No. 120 solvent oil and/or No. 150 solvent oil.
In the present invention, the solvent may be a protic solvent and/or an aprotic solvent.
According to the present invention, preferably, the curing conditions include: the temperature is 23 +/-2 ℃ and the humidity is 50 +/-10%.
The curing of the present invention is a conventional method in the field, and preferably, the curing may be performed after coating the reactant with a film; or pouring the reactants into a mould and curing.
The second aspect of the present invention provides a polyurethaneurea elastomer prepared by the above-described preparation method.
The third aspect of the present invention provides the use of the above-mentioned polyureide elastomer in waterproof coatings, sealants, adhesives, chemical grouting reinforcement materials and waterproof rolls.
Compared with the polyurethane material synthesized by the traditional polymeric polyol, the poly (ureide) elastomer has better hydrolysis resistance, solvent resistance and mechanical property; the invention can well make up the defects of the polyurethane material and keep the advantages of the polyurethane material. The poly (phenylurea) elastomer has wide application, and can be widely applied to waterproof coatings, sealants, adhesives, chemical grouting reinforcement materials and waterproof coiled materials.
The invention is further illustrated by the following examples:
the materials used in the following examples were all used in parts by mass.
Dibutyltin dilaurate used in the following examples was purchased from T-12 of air chemical products, Inc.; the dimer fatty acid was purchased from rainbow chemical Co., Ltd, Anqing, under the brand name HY-005; the trimerized fatty acid used was purchased from Polyalthia Sciensis GmbH under the designation BX-6; the carboxyl-terminated nitrile-butadiene liquid rubber is purchased from Zibo Qilong chemical Co., Ltd, and is under the brand number CTBN-25; the carboxyl acrylic resin is purchased from Zibozeyang chemical Co., Ltd, and the brand is ZY 01.
Example 1
Adding 11.5 parts of polycarbodiimide into a three-necked bottle, adding 5.3 parts of No. 150 solvent oil, and stirring for 2 hours at normal temperature; 4 parts of dimer fatty acid (weight average molecular weight of 560) and 0.02 part of dibutyltin dilaurate serving as a catalyst are added into the polycarbodiimide solution under the condition of strong stirring, and the stirring is continued for 10 minutes. Pouring into a grinding tool, and curing for 7 days at 23 + -2 ℃ under a standard environment with the humidity of 50 + -10%. And demolding and testing.
Wherein the polycarbodiimide is prepared by condensation reaction of toluene diisocyanate under catalysis of organic phosphine, and is blocked by monocyanate; the weight average molecular weight of the polycarbodiimide is 1704.
Example 2
Adding 18.4 parts of polycarbodiimide into a three-necked bottle, adding 5.3 parts of No. 150 solvent oil and 1 part of diisononyl phthalate (DINP), stirring for 2 hours at normal temperature, adding 8 parts of dimer fatty acid (with the weight-average molecular weight of 560), 1 part of trimer fatty acid (with the weight-average molecular weight of 900), 15 parts of No. 52 chlorinated paraffin and 6 parts of No. 150 solvent oil, and continuing stirring for 10 minutes under the condition of strong stirring. Pouring into a grinding tool, and curing for 7 days at 23 + -2 ℃ under a standard environment with the humidity of 50 + -10%. And demolding and testing.
Wherein the polycarbodiimide is prepared by condensation reaction of diphenylmethane diisocyanate under catalysis of organic phosphine, and is terminated by monocyanate; the polycarbodiimide had a weight average molecular weight of 1360.
Example 3:
adding 18 parts of polycarbodiimide curing agent into a three-necked bottle, adding 18 parts of butyl acetate, stirring at high speed for 1 hour at normal temperature, uniformly mixing, adding 55 parts of carboxyl-terminated butadiene-acrylonitrile liquid rubber (with the weight average molecular weight of 1500), and stirring at high speed for 10 minutes. Pouring into a grinding tool, and curing for 7 days at 23 + -2 ℃ under a standard environment with the humidity of 50 + -10%. And demolding and testing.
Wherein the polycarbodiimide is prepared by condensation reaction of toluene diisocyanate organic phosphine under catalysis, and is blocked by p-monoisocyanate; the weight average molecular weight of the polycarbodiimide was 1820.
Example 4
Adding 18 parts of polycarbodiimide curing agent into a three-necked bottle, adding 18 parts of butyl acetate, stirring at high speed for 1 hour at normal temperature, uniformly mixing, adding 1 part of dimer fatty acid (with the weight-average molecular weight of 560), 1.5 parts of methyl tetrahydrophthalic anhydride and 0.03 part of dibutyltin dilaurate serving as a catalyst, and stirring at normal temperature for 30 minutes. Pouring into a grinding tool, and curing for 7 days in a standard environment with the temperature of 23 +/-2 ℃ and the humidity of 80 +/-10%. And demolding and testing.
Wherein the polycarbodiimide is prepared by condensation reaction of toluene diisocyanate under catalysis of organic phosphine, and is blocked by p-monoisocyanate; the weight average molecular weight of the polycarbodiimide was 1820.
Example 5
Adding 21 parts of polycarbodiimide curing agent into a three-necked bottle, adding 5.3 parts of No. 150 solvent oil and 1 part of diisononyl phthalate (DINP), stirring for 2 hours at normal temperature, adding 5.7 parts of dimer fatty acid (with the weight-average molecular weight of 560), 1 part of trimer fatty acid (with the weight-average molecular weight of 900), 15 parts of No. 52 chlorinated paraffin and 6 parts of No. 150 solvent oil, and continuously stirring for 10 minutes under the condition of strong stirring. Pouring into a grinding tool, and curing for 7 days at 23 + -2 ℃ under a standard environment with the humidity of 50 + -10%. And demolding and testing.
Wherein the polycarbodiimide is prepared by condensation reaction of hexamethylene diisocyanate under catalysis of organic phosphine, and is blocked by monocyanate; the weight average molecular weight of the polycarbodiimide is 1760.
Example 6
And (2) adding 90 parts of polycarbodiimide curing agent into a three-necked bottle, adding 20 parts of butyl acetate, stirring at a high speed for 1 hour at normal temperature, uniformly mixing, adding 60 parts of carboxyl acrylic resin (with the weight-average molecular weight of 800), 8 parts of methyl tetrahydrophthalic anhydride, 20 parts of No. 52 chlorinated paraffin and 0.03 part of dibutyltin dilaurate serving as a catalyst, and stirring for 30 minutes at normal temperature. Pouring into a grinding tool, and curing for 7 days in a standard environment with the temperature of 23 +/-2 ℃ and the humidity of 80 +/-10%. And demolding and testing.
Wherein the polycarbodiimide is prepared by condensation reaction of toluene diisocyanate under catalysis of organic phosphine, and is blocked by p-monoisocyanate; the weight average molecular weight of the polycarbodiimide was 1820.
Test example
Mechanical property tests are carried out on the polyimide-based urea elastomers prepared in examples 1-6 according to GB/T19250-2013 standard, and specific test results are shown in Table 1.
TABLE 1
| Sample (I) | Tensile strength/MPa | Elongation at breakLength per cent |
| Example 1 | 10.57 | 190 |
| Example 2 | 3.83 | 245 |
| Example 3 | 1.51 | 350 |
| Example 4 | 6.47 | 237 |
| Example 5 | 4.37 | 278 |
| Example 6 | 8.57 | 230 |
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.
Claims (9)
1. A method for preparing a polyureide elastomer, comprising: uniformly mixing polycarbodiimide, polymer at least containing two acidic functional groups, chain extender, plasticizer, catalyst and solvent; then, curing is carried out to obtain the poly (phenylurea) elastomer;
the polymer containing at least two acidic functional groups is at least one of dimerized fatty acid, trimerized fatty acid and carboxyl acrylic resin;
the polycarbodiimide is derived from toluene diisocyanate and/or diphenylmethane diisocyanate and is blocked by monoisocyanate;
the chain extender is methyl tetrahydrophthalic anhydride;
the catalyst is dibutyltin dilaurate;
the plasticizer is selected from at least one of chlorinated paraffin, dioctyl phthalate, dibutyl phthalate, diisononyl phthalate, citrate plasticizer, vegetable oil plasticizer and polyether polyol;
the solvent is an organic solvent, and the organic solvent is at least one selected from 120# solvent oil, 150# solvent oil, ethyl acetate, butyl acetate, N, N-dimethylformamide and dimethyl sulfoxide;
the curing conditions comprise: the humidity was 50. + -. 10%.
2. The preparation method according to claim 1, wherein the polycarbodiimide is used in an amount of 8 to 99 parts, the polymer having at least two acidic functional groups is used in an amount of 1 to 92 parts, the chain extender is used in an amount of 0 to 10 parts, the plasticizer is used in an amount of 0 to 30 parts, the catalyst is used in an amount of 0 to 0.5 parts, and the solvent is used in an amount of 0 to 30 parts by mass.
3. The method according to claim 2, wherein the plasticizer is used in an amount of 5 to 30 parts and the solvent is used in an amount of 5 to 30 parts.
4. The production method as claimed in claim 1, wherein the polycarbodiimide has a weight average molecular weight of 500-3000.
5. The production method according to any one of claims 1 to 3, wherein the weight average molecular weight of the polymer having at least two acidic functional groups is 100-3500.
6. The production method according to claim 1, wherein the plasticizer is diisononyl phthalate.
7. The production method according to any one of claims 1 to 3, wherein the curing conditions include: the temperature is 23 +/-2oC。
8. A polyurethaneurea elastomer prepared by the process of any one of claims 1-7.
9. Use of the polyurethaneurea elastomer of claim 8 in waterproofing coatings, sealants, adhesives, chemical grouting reinforcements and waterproofing membranes.
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| DE19821666A1 (en) * | 1998-05-14 | 1999-11-25 | Basf Ag | Carbo-di:imide compounds, useful as hydrolytic stabilisers, especially for polyurethane elastomers containing ester units |
| DE10000656A1 (en) * | 2000-01-11 | 2001-07-12 | Basf Ag | New compatible hydrophilic compounds containing carbodiimide units and carboxyl or carboxylate groups are useful in increasing the molecular weight of aqueous polymer dispersions for use as adhesives or coatings |
| JP2004269691A (en) * | 2003-03-07 | 2004-09-30 | Nitto Denko Corp | Polycarbodiimides copolymer and its manufacturing process |
| EP2221331A1 (en) * | 2009-02-18 | 2010-08-25 | Sika Technology AG | Silane-terminated polyurethane polymers |
| US8778482B2 (en) * | 2012-09-28 | 2014-07-15 | Hewlett-Packard Indigo B.V. | Coated substrate and method for producing the same |
| KR20160124804A (en) * | 2014-02-20 | 2016-10-28 | 바스프 에스이 | Post-modified polycarbodiimides |
| JP6849268B2 (en) * | 2015-04-06 | 2021-03-24 | 日清紡ケミカル株式会社 | Modified polycarbodiimide compound, curing agent and thermosetting resin composition |
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| CN108715628B (en) * | 2018-06-22 | 2022-04-01 | 上海朗亿功能材料有限公司 | Alicyclic polycarbodiimide hydrolysis-resistant agent and preparation method thereof |
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