CN1081187A - Isocyanate-modified vinyl ester resin - Google Patents
Isocyanate-modified vinyl ester resin Download PDFInfo
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- CN1081187A CN1081187A CN 92108487 CN92108487A CN1081187A CN 1081187 A CN1081187 A CN 1081187A CN 92108487 CN92108487 CN 92108487 CN 92108487 A CN92108487 A CN 92108487A CN 1081187 A CN1081187 A CN 1081187A
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Abstract
A kind of isocyanate-modified vinyl ester resin of making by two-step reaction, it is characterized in that: a. reacts in the process of producing vinylester resin with unsaturated dibasic acid or the unsaturated monoprotic acid of its anhydride equivalent ground replacement 20～30mol% with epoxy compounds and unsaturated monoprotic acid in the presence of catalyzer and stopper, b. after finishing the building-up reactions of vinylester resin, promptly add isocyanic ester and carry out modification, and then dilute with vinylbenzene.The temperature of two secondary responses is respectively 80～150 ℃ and 60～130 ℃.Used catalyzer is amine or quaternary ammonium salt, particularly benzyl trimethyl ammonium chloride and benzyltriethylammoinium chloride; Used stopper is a phenolic compound, particularly Resorcinol and pyrocatechol.
Description
What the present invention relates to is isocyanate-modified vinyl ester resin.
Vinylester resin claims Epocryl again, it is a class new polymers of early sixties exploitation, normally pass through opening, again the constituent that forms with the vinylbenzene dilution by low-molecular-weight Resins, epoxy and the unsaturated monoprotic acid that with (methyl) vinylformic acid is representative.It can cause crosslinking reaction by means of superoxide, generates to have cancellated insoluble not melting property superpolymer.That is to say that this constituent is a kind of liquid material with proper viscosity, and can make it easily to solidify, thereby be used for reinforced plastics, be widely used at chemical industry lining, molding or aspects such as casted article, storage tank.But this material still can't fully satisfy many-sided service requirements like this at aspects such as physical strength, resistance toheat and chemical stabilities.
Poland Patent 110740(C.A.97: 7231n) once proposed a kind of have superior mechanical intensity and chemical stability, the isocyanate-modified vinyl ester resin of high heat resistance, it is characterized in that, earlier by epoxy compounds and the reaction of unsaturated monoprotic acid, obtain adduct, after being dissolved in vinylbenzene, react with isocyanate compound again.At this moment and since the part of hydroxyl in the adduct molecule by with the reaction of isocyanate compound by urethane, thereby improved mechanical property, thermotolerance and the chemical stability of final product.But also there is certain limitation in this method.At first, with unsaturated monoprotic acid and epoxy compounds reaction, reaction back molecular chain is an end-blocking, so that the Vinylite molecular weight that obtains is difficult to further raising, and the application performance of superpolymer is common and its molecular weight has confidential relation, promptly increases molecular weight and helps improving its physical strength, thermotolerance and chemical stability.Secondly, the vinylester resin that obtains after the vinylbenzene dilution, poor stability, glued easily when isocyanate-modified, modified-reaction is difficult to carry through to the end.
The present invention is intended to overcome the shortcoming of above-mentioned prior art, provides a kind of molecular weight ratio bigger, solidifies the back crosslinking degree again than higher isocyanate-modified vinyl ester resin.
Another object of the present invention is further to improve the performance of isocyanate-modified vinyl ester resin by the control of reaction process, makes it to realize suitability for industrialized production.
That is to say that isocyanate-modified vinyl ester resin provided by the invention is to be formed by two-step reaction by epoxy compounds, unsaturated monoprotic acid and isocyanic ester, it is characterized in that:
A. in the presence of catalyzer and stopper, produce in the process of vinylester resin, substitute the unsaturated monoprotic acid of part with unsaturated dibasic acid or its anhydride with epoxy compounds and the reaction of unsaturated monoprotic acid,
B. after finishing the building-up reactions of vinylester resin, promptly add isocyanate compound and carry out modification.And then dilute with vinylbenzene.
Substituting the unsaturated monacid purpose of part with unsaturated dibasic acid just is to overcome and after unsaturated monoprotic acid reacts with epoxy compounds the drawback that the molecular chain end-blocking is unfavorable for improving molecular weight takes place promptly.In addition,, therefore can improve the crosslinking degree behind the gained resin solidification, help improving the use propertieies such as physical strength, thermotolerance, chemical stability of resin because the functionality of unsaturated dibasic acid is bigger than unsaturated monoprotic acid.
Described epoxy compounds is meant the compound that contains two above epoxy group(ing) in the molecule, normally low-molecular-weight bisphenol A type epoxy resin, polyglycidyl ether etc.
Unsaturated monoprotic acid can be vinylformic acid, methacrylic acid, butenoic acid etc., and comparatively practical with acrylic or methacrylic acid.
Unsaturated dibasic acid and anhydride thereof comprise: diprotic acid and acid anhydrides thereof such as maleic acid, FUMARIC ACID TECH GRADE, m-phthalic acid, terephthalic acid.FUMARIC ACID TECH GRADE particularly, effect is obvious.
In building-up reactions, substitute the carboxyl equivalent of unsaturated monacid alternative amount with two kinds of acid in unsaturated dibasic acid, below 35mol% all can, but be preferably in 20～35mol% scope.This is to measure less than 20mol% because of substituting, and effect is just not obvious, is difficult to reach purpose of the present invention, otherwise, if the amount that substitutes greater than 35mol%, can cause the molecular resin amount that generates excessive, bring certain difficulty to synthesis technique, be that molecular weight is excessive, viscosity increases, and easily takes place glued.
In addition, the synthetic vinylester resin that obtains is dissolved in usually and is diluted in the vinylbenzene behind the resin solution for use, as described in the Poland Patent 110740.But because vinylbenzene itself has the autohemagglutination activity, therefore the resin solution less stable that obtains causes certain difficulty can for next step isocyanate-modified reaction.For example, temperature of reaction at this moment can not surpass 60 ℃, yet the speed of response of isocyanic ester is very slow under this temperature, is unfavorable for realizing suitability for industrialized production.In view of this, the present inventor finds by test, vinylbenzene diluted this step change into after isocyanate-modified and carry out, and can improve the temperature of modified-reaction and the stability of reaction system, helps realizing suitability for industrialized production.
That is to say that according to the present invention, the building-up reactions of vinylester resin can be carried out under 80～150 ℃, isocyanate-modified reaction can be carried out under 60～130 ℃.Temperature of reaction was controlled to hang down to be unfavorable for reacting and was carried through to the end, and prolongation reaction times or temperature of reaction control are too high, will cause double-bond polymerization and gluing.It is to be noted that especially in the second step reaction process, because the molecular weight of reactant is higher, the control of temperature of reaction is particularly important.
The isocyanic ester that is used for modification is meant that general formula is the compound of RNCO, adopts 2,4 toluene diisocyanate (TDI) and 4 usually, 4-'-diphenylmethane diisocyanate (MDI) etc.
The building-up reactions of vinylester resin is the reaction of a kind of epoxy group(ing) and carboxyl basically, and common available nucleophilic reagent is as catalyzer.Being applicable to of the present invention is amine or quarternary ammonium salt compound, particularly benzyl trimethyl ammonium chloride and benzyltriethylammoinium chloride, and consumption is in 0.4～0.8 weight part be advisable (is 100 weight parts with epoxy compounds).
In addition, test shows, if do not use stopper in reactive system, even temperature of reaction is no more than 100 ℃, also can cause double-bond polymerization and gluing, therefore for reaction can be carried out smoothly, and the stability of assurance products obtained therefrom, must adopt suitable stopper.Be applicable to that stopper of the present invention is a phenolic compound, Resorcinol particularly, pyrocatechol, consumption is in 0.04～0.1 weight part be advisable (is 100 weight parts with epoxy compounds).
The isocyanate-modified vinyl ester resin molecular-weight average of making by the present invention is about 850～900, and the molecular-weight average of the corresponding resin of making by Poland Patent 110740 is about 600～650.The good physical and chemical performance of the present invention's the existing Resins, epoxy of resin combination has the construction technology of unsaturated polyester resin self-vulcanizing again, is used for the anticorrosion of aspects such as chemical industry, building, and effect is fairly obvious.The resin of using the present invention as: Shanghai Bicycle Factory make pickling tank under 20% sulfuric acid and 90 ± 5 ℃ of envrionment conditionss, use continuously 3 years all right, the life-span has been improved nearly 5 times than former use Resins, epoxy.Machine two factories in Shanghai use resin manufacture fiberglass blower fan blade of the present invention, have in light weight, intensity is high, moisture-proof is warm, the characteristics of long service life.
The invention will be further described below in conjunction with embodiment." part " in each example all refers to " weight part ".
Embodiment one:
In the container that is equipped with agitator, drop into 100 parts of lower molecular weight bisphenol A type epoxy resins, 30 parts in vinylformic acid, 7 parts of fumaroyls under the condition that 0.4 part of benzyl trimethyl ammonium chloride and 0.08 part of existence of Resorcinol are arranged, stirred about 3 hours down at 100 ± 5 ℃, when the survey acid number to 30 of waiting to sample is following (mg KOH/g), add TDI10 part, reacted 2 hours down at 80 ℃, after the cooling, with 76 parts of vinylbenzene dilutions, be referred to as the M-1 resin.In addition, except that substitute 30 parts of vinylformic acid and 7 parts of FUMARIC ACID TECH GRADE with 40 parts of vinylformic acid, all the other all same as described above not making substitute the unsaturated monacid isocyanate-modified vinyl ester resin of part with unsaturated dibasic acid, are referred to as the N-1 resin.Cooperate routinely respectively with these two kinds of resins and to make casting matrix, being compared as follows shown in the table of its mechanical property.
M-1 resin N-1 resin
Tensile strength, MPa 69 60
Compressive strength, MPa 97 87
Flexural strength, MPa 98 94
Heat-drawn wire, ℃ 110 83
Solidify post-shrinkage ratio, % 5～6 5～6
Unit elongation, % 5.48 3.8
Degree of cure, % 92 87
Ba Ke hardness 38 35
Above-mentioned M-1 resin and being compared as follows shown in the table not with isocyanate-modified general vinylester resin erosion resistance.
| Medium | The M-1 resin | Unmodified vinylester resin | ||||
| Appearance change | Changes in weight % | The corrosion resistant grade | Appearance change | Changes in weight % | The corrosion resistant grade | |
| NaOH 30％ | Loss of gloss is arranged slightly | ＋0.402 | Ⅰ | Turn white, be clamminess in the surface | ＋5.671 | Not anti- |
| H 2SO 450％ | There is not big the variation | －0.18 | Ⅰ | Brown, the loss of gloss in surface | －4.927 | Ⅲ |
| HCl 31％ | There is not big the variation | －0.09 | Ⅰ | Surface resin comes off | －3.983 | Ⅱ |
Annotate: test conditions: 80 ℃ * 300h
Embodiment two:
Except substituting 10 parts of TDI with 8 parts of MDI, and FUMARIC ACID TECH GRADE changes 8 into especially, all the other are all identical with the M-1 resin method for making described in the embodiment one, the isocyanate-modified vinyl ester resin solution that obtains, behind peroxide cure, show excellent chemical stability, thermotolerance and physical strength preferably equally.
Embodiment three:
In the container that is equipped with agitator, drop into 100 parts of low-molecular-weight polyglycidyl ethers, 28 parts of methacrylic acids, 7 parts of MALEIC ANHYDRIDE are having in the presence of 0.08 part of 0.5 part of benzyltriethylammoinium chloride and the pyrocatechol, 150 ℃ of following stir abouts 1.5 hours, when treating that acid number to 30 following (mg KOH/g) is surveyed in sampling, add TDI10 part, reaction is 3 hours under 60 ℃, the cooling back gets liquid product with 75 parts of vinylbenzene dilutions.After this product cooperates curing routinely, have excellent chemical stability and physical strength.
Embodiment four:
In the container that is equipped with agitator, drop into 100 parts of lower molecular weight bisphenol A type epoxy resins, 32 parts in vinylformic acid, 8 parts of m-phthalic acids, having in the presence of 0.06 part of 0.4 part of benzyl trimethyl ammonium chloride and the Resorcinol, 80 ℃ of following stir abouts 4～5 hours, when sampling survey acid number reaches (mg KOH/g) below 30, adding MDI8 part was reacted about 1.5 hours down at 130 ℃, and dilute with 78 parts of vinylbenzene the cooling back, this product cured strength height, good heat resistance.
Claims (5)
1, a kind of isocyanate-modified vinyl ester resin that is formed by epoxy compounds, unsaturated monoprotic acid and isocyanate reaction is characterized in that:
A. in the presence of catalyzer and stopper, produce in the process of vinylester resin, substitute the unsaturated monoprotic acid of part with unsaturated dibasic acid or its anhydride with epoxy compounds and the reaction of unsaturated monoprotic acid,
B. after finishing the building-up reactions of vinylester resin, promptly add isocyanate compound and carry out modification, and then dilute with vinylbenzene.
2, isocyanate-modified vinyl ester resin as claimed in claim 1 is characterized in that, in described vinylester resin building-up reactions, with the alternative unsaturated monoprotic acid of 20～35mol% of the unsaturated dibasic acid of equivalent.
3, as claim 1,2 described isocyanate-modified vinyl ester resins is characterized in that, the synthesis reaction temperature of described vinylester resin is 80～150 ℃, and the temperature of isocyanate-modified reaction is 60～130 ℃.
4, as claim 1,2 described isocyanate-modified vinyl ester resins is characterized in that, the catalyzer that uses in the reaction is amine or quaternary ammonium salt, particularly benzyl trimethyl ammonium chloride, benzyltriethylammoinium chloride.
5, as claim 1,2 described isocyanate-modified vinyl ester resins is characterized in that used stopper is a phenolic compound in the reaction, particularly Resorcinol, pyrocatechol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92108487 CN1029924C (en) | 1992-07-06 | 1992-07-06 | isocyanate-modified vinyl ester resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92108487 CN1029924C (en) | 1992-07-06 | 1992-07-06 | isocyanate-modified vinyl ester resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1081187A true CN1081187A (en) | 1994-01-26 |
| CN1029924C CN1029924C (en) | 1995-10-04 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 92108487 Expired - Fee Related CN1029924C (en) | 1992-07-06 | 1992-07-06 | isocyanate-modified vinyl ester resin |
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| Country | Link |
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| CN (1) | CN1029924C (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100334125C (en) * | 2002-06-28 | 2007-08-29 | 兰州思特创新科技有限责任公司 | High temperature corrosion-resisting resin |
| CN100358931C (en) * | 2005-11-18 | 2008-01-02 | 华东理工大学华昌聚合物有限公司 | Tech. for synthesizing high toughness epoxy vinyl ester resin |
| CN101205290B (en) * | 2007-11-30 | 2010-04-21 | 华南理工大学 | Isocyanate modified epoxy acrylic ester and preparation thereof |
| CN116143997A (en) * | 2023-03-14 | 2023-05-23 | 山东凯威尔新材料有限公司 | Preparation method of epoxy vinyl resin with enhanced mechanical properties |
-
1992
- 1992-07-06 CN CN 92108487 patent/CN1029924C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100334125C (en) * | 2002-06-28 | 2007-08-29 | 兰州思特创新科技有限责任公司 | High temperature corrosion-resisting resin |
| CN100358931C (en) * | 2005-11-18 | 2008-01-02 | 华东理工大学华昌聚合物有限公司 | Tech. for synthesizing high toughness epoxy vinyl ester resin |
| CN101205290B (en) * | 2007-11-30 | 2010-04-21 | 华南理工大学 | Isocyanate modified epoxy acrylic ester and preparation thereof |
| CN116143997A (en) * | 2023-03-14 | 2023-05-23 | 山东凯威尔新材料有限公司 | Preparation method of epoxy vinyl resin with enhanced mechanical properties |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1029924C (en) | 1995-10-04 |
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