CN107189028B - Environment-friendly high-performance rapid demoulding polyurethane reaction injection molding composition and preparation method of autocatalysis chain extender thereof - Google Patents
Environment-friendly high-performance rapid demoulding polyurethane reaction injection molding composition and preparation method of autocatalysis chain extender thereof Download PDFInfo
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Abstract
The invention discloses an environment-friendly high-performance rapid demoulding polyurethane reaction injection molding composition and a preparation method of an autocatalysis chain extender thereof. The composition comprises two components, wherein the component A comprises 1-10% of an autocatalytic chain extender and 0.01-2% of a composite catalyst, and the autocatalytic chain extender is a substance with the following structure:
wherein x is 2 to 5 and R is CyH2y+1Y is 0-2; the composite catalyst comprises 10 parts of bismuth isooctanoate, 1-2 parts of potassium isooctanoate, 15 parts of bicyclic amidine compounds and 10 parts of glycerol. And B component: 60-95% of MDI, 5-40% of modifier and NCOIn an amount of 23% to 28%, the modifier comprises at least one diol and at least one triol. The preparation method of the self-catalytic chain extender comprises the steps of heating anhydrous piperazine to 65 +/-5 ℃, slowly dripping one of ethylene oxide, propylene oxide or butylene oxide into a reaction container according to a molar ratio under a constant temperature state, heating to 80-85 ℃ after dripping is finished, reacting for 4 hours, cooling and discharging. The composition has the advantages of low odor, low VOC, good weather resistance and short demoulding time.
Description
Technical Field
The invention relates to a polyurethane reaction injection molding material and a preparation process thereof.
Background
Polyurethane reaction injection molding (PU-RIM) materials are widely used in automobiles, and distinguish major interior and exterior parts from application sites. Materials in an automobile cockpit belong to interior trim parts, such as automobile seat foam, and the requirements of the products on the environmental protection performance of the materials, such as odor grade, volatile organic matter content and the like, are very strict; the parts outside the cockpit are automobile exterior parts, such as a skylight, a large enclosure and the like, so that the requirements on the light aging performance of the material are more strict, and the requirements on the environmental protection performance are relatively low. However, with the continuous update and upgrading of products and the continuous improvement of the requirements on the products, many products have double high requirements on the weather resistance and the environmental protection performance of materials, wherein the PU-RIM material for automobile glass wrapping is more typical, the material belongs to an exterior trimming part and needs higher weather resistance, and meanwhile, the requirement on the environmental protection performance is increasingly improved because the PU-RIM material is directly connected with a cockpit. Therefore, the reduction of the content of volatile organic compounds and the reduction of odor under the premise of ensuring high reactivity and high weather resistance are the main problems of the materials at present.
The polyurethane material can be divided into two main classes of aromatic and aliphatic according to different isocyanate, and the aromatic isocyanate is used as the traditional polyurethane raw material and is widely and deeply applied. However, the aromatic isocyanate contains benzene rings in the structure, so that the aromatic isocyanate is easy to react and turn yellow under the action of light; the aliphatic isocyanate has excellent light aging resistance, but the reaction activity of the aliphatic isocyanate is low, so that the requirements of PU-RIM on gel and demolding time are difficult to meet.
Patent documents CN1633454A, CN1455791A, CN1946756A, CN101061154A, and CN101906200 all relate to technologies for producing polyurethane materials by using autocatalytic polyols, but all need to be matched with other amine catalysts, the technical application range belongs to polyurethane foaming materials, and the reaction speed and the molecular structure of the polyurethane foaming materials are not suitable for a reaction injection molding process; in addition, the polyol has high viscosity, poor flowability and poor mold filling property, and cannot be directly applied to a non-foaming system because a large amount of foaming agent or water is required to be used.
Patent document CN103172822A discloses a rapid demoulding weather-proof polyurethane reaction injection molding composition and a preparation method thereof. By using the organic metal composite catalyst, the reaction rate can be obviously improved, the gelling time and the demolding time are greatly shortened, the gelling time is 8-20 s, and the demolding time is 45-600 s. The method can realize higher production efficiency, but because the composite catalyst contains a certain amount of solvent, such as acetone, 1, 4-dioxane, xylene or ethyl acetate, and the composite catalyst accounts for a larger proportion in a composition system, the odor grade and VOC of the material cannot meet the requirements of the application field on environmental protection performance.
Disclosure of Invention
The invention aims to solve the first technical problem of providing an environment-friendly high-performance rapid demoulding polyurethane reaction injection molding composition which has low smell, low VOC, good weather resistance and short demoulding time.
The second technical problem to be solved by the invention is to provide a preparation method of the self-catalytic chain extender used by the composition. The self-catalytic chain extender has high catalytic activity and can be matched with aliphatic isocyanate for use.
In order to solve the first technical problem, the invention provides an environment-friendly high-performance quick-demolding polyurethane reaction injection molding composition, which comprises A, B two components, and the composition comprises the following components in parts by mass:
the component A comprises: 50-90% of polyether polyol, 1-10% of self-catalysis chain extender, 1-10% of chain extender, 1-20% of cross-linking agent, 0-8% of pigment, 1-5% of anti-aging agent and 0.01-2% of composite catalyst, preferably 0.5-2%;
and B component: 60-95% of 4, 4' -dicyclohexyl methane diisocyanate, 5-40% of modifier and 23-28% of isocyanato (NCO). The modifier comprises at least one dihydric alcohol and at least one trihydric alcohol. The dihydric alcohol comprises one or more of polyoxypropylene diol, polytetrahydrofuran diol and the like, wherein the molecular weight of the polyoxypropylene diol is preferably 400-4000, and the molecular weight of the polytetrahydrofuran diol is preferably 650-2000. The trihydric alcohol is preferably one or more of trimethylolethane, trimethylolpropane, glycerol, and the like.
The self-catalytic chain extender is a substance with the following structure:
wherein x is 2 to 5 and R is CyH2y+1，y＝0～2。
The composite catalyst is prepared by compounding bismuth isooctanoate, potassium isooctanoate, dicycloamidine compounds and glycerol, and the compounding mass ratio is as follows: 10 parts of bismuth isooctanoate, 1-2 parts of potassium isooctanoate, 15 parts of bicyclic amidine compounds and 10 parts of glycerol, wherein the bicyclic amidine compounds have the following general formula:
in the formula R1＝CaH2a，a＝2～4；R2＝CbH2b，b＝3～7。
The suitable polyether polyol is preferably one or more of ethylene oxide-propylene oxide copolyether triol with primary hydroxyl content of more than 70 percent and number average molecular weight of 3000-6500.
Suitable chain extenders are preferably one or more of ethylene glycol, 1, 4-butanediol, 1, 3-butanediol, diethylene glycol, diethanolamine, and the like.
Suitable crosslinking agents are preferably one or more of glycerol, trimethylolethane, trimethylolpropane, trishydroxyethyl isocyanurate, and the like.
Suitable anti-aging agents are preferably one or more of 2- (2 ' -hydroxy-3 ', 5 ' -di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2 ' -hydroxy-5 ' -methylphenyl) benzotriazol-ide, bis (3, 5-tert-butyl-4-hydroxyphenyl) sulfide, bis (1, 2, 2, 6, 6-pentamethyl-4-piperidinyl) sebacate, trioctyl phosphite, and the like.
A method of making the composition of the present invention, comprising:
the component A comprises: adding the materials into a reaction kettle, and uniformly mixing at 25 ℃.
And B component: and adding the isocyanate and the modifier into a reaction vessel simultaneously, heating to 90 ℃ while stirring, reacting for 2-3 h, cooling to room temperature, and discharging.
The autocatalysis type chain extender can be prepared by alkoxylating piperazine and one of ethylene oxide, propylene oxide or butylene oxide, and the reaction formula is as follows:
wherein n, m, h is 2-5.
The product is represented by the general formula:
wherein x is 2 to 5 and R is CyH2y+1，y＝0～2。
In order to solve the second technical problem, the invention provides a method for preparing an autocatalytic chain extender, which comprises the following steps: heating anhydrous piperazine in a reaction container with a condensation reflux device to 65 +/-5 ℃, slowly dripping one of ethylene oxide, propylene oxide or butylene oxide into the reaction container according to a molar ratio under a constant temperature state, heating to 80-85 ℃ after dripping is finished, reacting for 4 hours, cooling to room temperature, and discharging.
Compared with the prior art, the composition has the following beneficial effects:
1. the self-catalytic chain extender reduces the dosage of the catalyst under the condition of ensuring the reaction speed with the aliphatic isocyanate, and does not contain any organic solvent and amine catalyst. Compared with CN103172822A in the prior art, the use amount of the composite catalyst can be reduced by 20-30%, so that the composite catalyst has lower odor and VOC and better environmental protection.
2. The self-catalysis chain extender can effectively improve the reaction activity of a system, the composite catalyst and the self-catalysis chain extender have certain thermal sensitivity, the higher the temperature is, the better the catalytic effect on polymerization is, and the heat release in the polyurethane polymerization process is obvious, so that the reaction of the composition has better self-acceleration effect, the gel and demolding time is shortened, and the reaction rate can be effectively improved. Compared with the prior art CN103172822A, the production efficiency is higher.
3. The special structure of the autocatalytic chain extender is applied in the formula of the composition, so that the generation of urea groups can be improved in the reaction, the crosslinking degree is improved, and the mechanical property of a polymer material can be improved. Compared with CN103172822A in the prior art, the material has higher mechanical property.
4. The composition does not contain solvent and amine catalyst, and the total use amount of the composite catalyst can be greatly reduced due to the existence of the autocatalytic chain extender, and compared with CN103172822A in the prior art, the use amount of the composite catalyst can be reduced by 20-30%, so that the composition has lower odor and VOC, and better environmental protection.
In conclusion, the composition has the advantages of high reactivity and short demoulding time, and can be used for preparing a high-performance polyurethane material by a Reaction Injection Molding (RIM) process, and the obtained material has low odor, low VOC and good weather resistance.
Detailed Description
The present invention is further illustrated by the following examples, in which the parts are by mass.
Example 1
(1) Synthesizing an autocatalytic chain extender: heating anhydrous piperazine in a reaction container with a condensation reflux device to 65 ℃, dropwise adding propylene oxide into the reaction container according to the molar ratio of piperazine to propylene oxide being 1: 4 under the constant temperature state, heating to 80-85 ℃ after dropwise adding, reacting for 4h, cooling to room temperature, and discharging. The structure of the product obtained by the reaction is as follows:
(2) preparing a composite catalyst: 10 parts of bismuth isooctanoate, 1 part of potassium isooctanoate, 15 parts of dicycloamidine compounds and 10 parts of glycerol are fully stirred and uniformly mixed for later use.
(3) Preparation of the composition
330N: ethylene oxide-propylene oxide copolyether triol having a hydroxyl value of 33.5 to 36.5mgKOH/g
The component A comprises: 330N, 77.5 parts, 8 parts of the prepared autocatalytic chain extender, 4 parts of ethylene glycol, trimethylolpropane: 8 parts of carbon black: 0.5 part of 2- (2 '-hydroxy-5' -methylphenyl) benzotriazole: 0.6 part of bis (3, 5-tertiary butyl-4-hydroxyphenyl) sulfide: 0.4 part of composite catalyst and 1 part of composite catalyst.
And B component: 4, 4' -dicyclohexylmethane diisocyanate, 90.3 parts, polytetrahydrofuran diol (molecular weight 1000): 7.5 parts, trimethylolpropane: 2.2 parts. The NCO mass fraction was 26.2%.
(4) Example composition A, B A process for preparing a PU-RIM material by a high pressure injection machine was as follows:
① feeding, adding the component A into the tank A of the high-pressure machine and adding the component B into the tank B of the high-pressure machine;
② injection, wherein the material temperature of the component A is set to be 30-45 ℃, the material temperature of the component B is set to be 30-45 ℃, the injection pressure is 15 +/-3 MPa, and the material is injected into a mold with the mold temperature being heated to 110-120 ℃.
③ demoulding, namely demoulding for 40s when the gelling time is less than or equal to 10s, and demoulding for 90s when the gelling time is 10-15 s.
④ post-curing, namely curing for 1 hour at 80 ℃.
Comparative example
The preparation process of the comparative example material is the same as that of the example, the composition components are different, and the autocatalytic chain extender and the composite catalyst are not added.
The component A comprises: 330N, 76.5 parts, 10 parts of ethylene glycol, trimethylolpropane: 10 parts of carbon black: 0.5 part of 2- (2 '-hydroxy-5' -methylphenyl) benzotriazole: 0.6 part of bis (3, 5-tertiary butyl-4-hydroxyphenyl) sulfide: 0.4 part, and 2 parts of composite catalyst in a comparative patent CN 103172822A.
And B component: 4, 4' -dicyclohexylmethane diisocyanate, 90.3 parts, polytetrahydrofuran diol (molecular weight 1000): 7.5 parts, trimethylolpropane: 2.2 parts. The NCO mass fraction was 26.2%.
TABLE 1 comparison of the Properties of the materials of the examples and comparative examples
Claims (5)
1. An environment-friendly high-performance quick-release polyurethane reaction injection molding composition comprises A, B two components, and comprises the following components in parts by mass:
the component A comprises: 50-90% of polyether polyol, 1-10% of self-catalysis chain extender, 1-10% of chain extender, 1-20% of cross-linking agent, 0-8% of pigment, 1-5% of anti-aging agent and 0.01-2% of composite catalyst;
and B component: 60-95% of 4, 4' -dicyclohexyl methane diisocyanate, 5-40% of modifier and 23-28% of isocyanato (NCO); the modifier comprises at least one dihydric alcohol and at least one trihydric alcohol; the dihydric alcohol refers to polyoxypropylene diol or polytetrahydrofuran diol and a mixture thereof; the trihydric alcohol is selected from one or more of trimethylolethane, trimethylolpropane and glycerol;
the self-catalytic chain extender is prepared by the following method: heating anhydrous piperazine in a reaction container with a condensation reflux device to 65 +/-5 ℃, slowly dropwise adding one of ethylene oxide, propylene oxide or butylene oxide into the reaction container in a constant temperature state according to the amount which is 4 times of the molar number of the piperazine, heating to 80-85 ℃ after dropwise adding, reacting for 4 hours, cooling to room temperature, and discharging;
the chain extender is one or more selected from ethylene glycol, 1, 4-butanediol, 1, 3-butanediol, diethylene glycol and diethanolamine;
the composite catalyst is prepared by compounding bismuth isooctanoate, potassium isooctanoate, dicycloamidine compounds and glycerol, and the compounding mass ratio is as follows: 10 parts of bismuth isooctanoate, 1-2 parts of potassium isooctanoate, 15 parts of bicyclic amidine compounds and 10 parts of glycerol, wherein the bicyclic amidine compounds have the following general formula:
in the formula R1＝CaH2a，a＝2～4；R2＝CbH2b，b＝3～7。
2. The composition according to claim 1, wherein the polyoxypropylene diol has a molecular weight of 400-4000 and the polytetrahydrofuran diol has a molecular weight of 650-2000.
3. The composition as claimed in claim 1, wherein the polyether polyol is one or more selected from ethylene oxide-propylene oxide copolyether triols having a primary hydroxyl group content of > 70% and a number average molecular weight of 3000 to 6500.
4. Composition according to claim 1, characterized in that the crosslinking agent is selected from one or more of glycerol, trimethylolethane, trimethylolpropane, trishydroxyethyl isocyanurate.
5. The composition of claim 1, wherein the anti-aging agent is selected from one or more of 2- (2 ' -hydroxy-3 ', 5 ' -di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2 ' -hydroxy-5 ' -methylphenyl) benzotriazol-e, bis (3, 5-tert-butyl-4-hydroxyphenyl) sulfide, bis (1, 2, 2, 6, 6-pentamethyl-4-piperidinyl) sebacate, and trioctyl phosphite.
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