CN113024770B - Preparation method of high-strength high-toughness vinyl ester resin - Google Patents
Preparation method of high-strength high-toughness vinyl ester resin Download PDFInfo
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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Abstract
The invention relates to a preparation method of a high-strength high-toughness vinyl ester resin, which comprises the following steps: firstly, diisocyanate and polyether diol react to prepare isocyanate-terminated polyurethane Prepolymer (PUR), then the polyurethane Prepolymer (PUR) reacts with hydroxyl of epoxy resin to obtain polyurethane segmented modified epoxy resin (UE), and finally the polyurethane segmented modified epoxy resin (UE) reacts with unsaturated monocarboxylic acid to obtain polyurethane modified Vinyl Ester Resin (VER). The preparation method of the invention not only blocks the flexible polyether chain segment into the resin structure, but also increases the functionality of the vinyl ester resin due to the existence of the urethane bond. Therefore, after the high-strength high-toughness vinyl ester resin is cured, the shrinkage rate is low, the strength is high, the impact resistance is obviously improved, the comprehensive performance is good, the product is stable, and the reaction route is reasonable.
Description
Technical Field
The invention relates to a preparation method of a high-strength and high-toughness vinyl ester resin, belonging to the field of vinyl ester resins.
Background
Vinyl resin, also known as epoxy acrylate resin, is prepared by ring-opening addition of epoxy resin and monounsaturated carboxylic acid, and then dissolved in unsaturated polymerizable monomer to obtain vinyl ester resin. The vinyl ester resin has outstanding corrosion resistance, mechanical property, construction process property, cost performance and the like, and has been the name of super anticorrosive resin.
Although vinyl ester resins have gained a great deal of popularity in traditional anticorrosion applications and engineering applications, conventional vinyl ester resins have some disadvantages: the vinyl ester resin has large curing shrinkage, and the cured product has more rigidity but insufficient toughness. In the case where the vinyl ester resin is required to have high impact resistance and elongation at break, for example, tough glass fiber reinforced plastics, sports equipment, automobile parts, and the like are limited to a certain extent. Therefore, the synthesis of a high-strength vinyl ester resin with excellent impact resistance is required to have important application value, so that the vinyl ester resin can be applied to a plurality of downstream fields.
Patent 201911206917.6 discloses a toughened modified vinyl ester resin and a synthesis method thereof, firstly, diisocyanate and flexible dihydric alcohol are adopted in a reaction kettle to prepare an isocyanate-terminated polyurethane prepolymer under the action of a catalyst A; meanwhile, in the other reaction kettle, epoxy resin and unsaturated monocarboxylic acid are reacted under the action of a catalyst B and a polymerization inhibitor to obtain the non-toughened vinyl ester resin. And finally, adding isocyanate-terminated polyurethane prepolymer and a catalyst A into the vinyl ester resin to prepare the polyurethane toughening modified vinyl ester resin. Patent 201410004706.5 discloses a high activity vinyl ester resin gel coat and a preparation method thereof, firstly, epoxy resin and unsaturated monobasic acid/anhydride and/or dicarboxylic acid/anhydride react to obtain vinyl ester resin with terminal hydroxyl, meanwhile, diol and/or polyol with low molecular weight and isocyanate are adopted to prepare polyurethane prepolymer, and finally, the polyurethane prepolymer is used for graft modification to prepare the high activity vinyl ester resin. The synthetic route of the invention is to firstly toughen and modify the epoxy resin by adopting polyurethane prepolymer and then prepare vinyl ester resin, while the domestic patent synthetic route is to toughen the epoxy resin by adopting the polyurethane prepolymer and unmodified vinyl ester resin to carry out grafting reaction. Experiments prove that the existing synthetic route has the following defects: (1) The reaction temperature of the polyurethane prepolymer and vinyl ester is generally 50-60 ℃, the reaction is safe, the reaction is difficult to complete under the condition of not adding a catalyst due to low reaction temperature, but the stability of an ester group on the vinyl ester resin is influenced after the catalyst is added, and the reaction time is generally more than 3 hours; (2) Firstly, synthesizing unmodified vinyl ester resin, wherein a molecular chain of the unmodified vinyl ester resin is provided with a plurality of hydroxyl groups (side hydroxyl groups of epoxy and hydroxyl groups of epoxy ring opening), and then reacting the unmodified vinyl ester resin with a polyurethane prepolymer, wherein the regularity of a reaction product is poor; (3) The addition amount of the polyurethane prepolymer is limited, the polyurethane prepolymer is easy to gel when being added by 12 percent, and the shelf life of the product is short. (4) When the addition amount of the polyurethane prepolymer is the same, the viscosity of the polyurethane prepolymer graft modified vinyl ester resin is higher.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and discloses a preparation method of a high-strength high-toughness vinyl ester resin.
The technical scheme of the invention is as follows: a preparation method of a high-strength high-toughness vinyl ester resin comprises the following steps:
step 1: a polyurethane prepolymer synthesis step comprising:
adding polyether glycol into a reaction bottle, stirring, introducing nitrogen for protection, heating the reaction bottle to 70-90 ℃, adding diisocyanate into a constant-pressure dropping funnel, dropping at the speed of 1-3 d/s, reacting at the constant temperature of 80-100 ℃ after the diisocyanate is dropped, measuring the content of NCO by adopting a method of national standard HG/T2409-92, and stopping the reaction when the content of NCO reaches a theoretical value to obtain a polyurethane Prepolymer (PUR) for later use;
step 2: the synthesis method of the polyurethane prepolymer modified epoxy resin comprises the following steps:
adding the polyurethane Prepolymer (PUR) into a reaction bottle, stirring, introducing nitrogen for protection, heating the reaction bottle to 80-90 ℃, adding epoxy resin in batches, heating to 90-110 ℃ for continuous reaction after reacting for 0.5-1h, and stopping the reaction when the NCO content is 0-0.05%, thus obtaining polyurethane prepolymer modified epoxy resin (UE) for later use;
and step 3: the synthesis method of the high-strength and high-toughness vinyl ester resin comprises the following steps:
adding the polyurethane prepolymer modified epoxy resin (UE) into a reaction bottle, stirring, heating to 75-85 ℃, dissolving unsaturated monocarboxylic acid, a catalyst and a polymerization inhibitor, adding into a constant-pressure dropping funnel, dropwise adding at a speed of 1-2d/s, slowly heating to 90-100 ℃, reacting at a constant temperature until the acid value of the system is reduced to below 8mg/gKOH, cooling to below 80 ℃, adding 0.1-0.2% of solid paraffin and 30-40% of styrene monomer to ensure that the solid content of the resin is 60-70%, and stirring uniformly to finally obtain the high-strength toughened Vinyl Ester Resin (VER) with more than 2 functional groups.
Preferably, the polyether diol is one or more of polyoxypropylene diol PPG600, PPG1000 and PPG 2000.
Further, the polyether glycol is dehydrated in advance.
Preferably, the diisocyanate is one or more of Toluene Diisocyanate (TDI), diphenylmethane-4, 4' -diisocyanate (MDI), hexamethylene 1, 6-diisocyanate (HDI), isophorone diisocyanate (IPDI), and Xylylene Diisocyanate (XDI).
Preferably, the epoxy resin is one or more of E54, E51, E44 and E42.
Further, the epoxy resin is dehydrated in advance.
Preferably, the unsaturated monocarboxylic acid is one or more of acrylic acid and methacrylic acid.
Preferably, the catalyst is one or more of benzyldimethylamine, benzyltrimethylammonium chloride, benzyltriethylammonium chloride, triphenylphosphine and triphenylphosphine chloride.
Preferably, the polymerization inhibitor is one or more of hydroquinone, p-tert-butylcatechol, 2, 6-di-tert-butyl-p-methylphenol, p-benzoquinone, p-hydroxy-semi-benzoquinone and 2, 3-dichloro-1, 4-naphthoquinone.
The invention has the beneficial effects that: after the high-strength high-toughness vinyl ester resin prepared by modification is cured, the volume shrinkage rate of a resin casting body is obviously reduced, the toughness is obviously improved, the elongation at break is more than 10%, the impact strength is good, the bonding performance and the strength are also improved to a certain extent, the comprehensive performance is good, and the product is stable.
Detailed Description
The invention will be further illustrated with reference to the following specific examples:
the synthetic technical route of the high-strength high-toughness vinyl ester resin is as follows:
as can be seen from the above reaction formulas, the second step of the synthetic technical route of the present invention is to react the isocyanate-terminated groups of the polyurethane prepolymer with the pendant hydroxyl groups of the epoxy resin backbone to form a high strength toughened epoxy resin (UE) with theoretically 4 functional groups. In the reaction, the-NCO of the polyurethane prepolymer reacts with the epoxy resin side-OH without adding a catalyst, the polyurethane prepolymer has high addition amount and is not easy to generate side reactions such as gel and the like, the reaction can be completed when the temperature is increased to 80 to 110 ℃, and the product has strong regularity, which shows that the product has higher mechanical property.
The third step of the synthetic technical route of the invention takes monocarboxylic acid as a nucleophilic reagent to attack the terminal carbon atom (C) in the epoxy group which shows a positive valence state, so that the epoxy group is subjected to ring opening to generate an ester bond, and the high-strength high-toughness Vinyl Ester Resin (VER) is obtained.
Because the regularity of the product in the second step is good, and the influence of additives such as a catalyst and the like is avoided, the reaction condition in the third step is easy to control, the reaction temperature is 90-100 ℃, the gel phenomenon is not easy to generate in the reaction process, the regularity of the synthesized high-strength high-toughness Vinyl Ester Resin (VER) is good, the viscosity is low under the same solid content, and the product has excellent mechanical properties.
Other domestic patents adopt polyurethane prepolymer to directly toughen and modify vinyl ester resin, under the action of a catalyst, the-NCO of the polyurethane prepolymer reacts with epoxy side hydroxyl and epoxy ring-opening hydroxyl on the vinyl ester resin, even a small amount of hydroxyl is self-polymerized to generate allophanate and the like, the regularity of a product is poor, and ester groups in the vinyl ester resin are unstable, so that the product is complex and the reaction controllability is poor.
The mechanism of the invention is as follows: the invention firstly prepares isocyanate-terminated polyurethane Prepolymer (PUR) by reacting diisocyanate with polyether diol, then reacts the polyurethane Prepolymer (PUR) with hydroxyl of epoxy resin to obtain polyurethane segmented modified epoxy resin (UE), and finally reacts with unsaturated monocarboxylic acid to obtain polyurethane modified Vinyl Ester Resin (VER). The preparation method of the invention not only blocks the flexible polyether chain segment into the resin structure, but also increases the functionality of the vinyl ester resin due to the existence of the urethane bond. Therefore, after the high-strength high-toughness vinyl ester resin is cured, the shrinkage rate is low, the strength is high, the impact resistance is obviously improved, the comprehensive performance is good, the product is stable, and the reaction route is reasonable.
Example 1
The preparation method of the high-strength high-toughness vinyl ester resin comprises the following steps:
step 1: a polyurethane prepolymer synthesis step comprising:
adding 300g of polyether glycol PPG2000 into a reaction bottle, stirring, introducing nitrogen for protection, heating the reaction bottle to 80 ℃, adding 54.6g of TDI into a constant-pressure dropping funnel, dropping at the speed of 2d/s, reacting at the constant temperature of 90 ℃ after the TDI is dropped, measuring the-NCO content to be 3.88% by adopting a method of national standard HG/T2409-92, stopping the reaction when the theoretical value is reached, and obtaining a polyurethane Prepolymer (PUR) for later use.
Step 2: the synthesis method of the polyurethane prepolymer modified epoxy resin comprises the following steps:
454.6g of polyurethane Prepolymer (PUR) is added into a reaction bottle and stirred, nitrogen is introduced for protection, the reaction bottle is heated to 90 ℃, 461.4g of epoxy resin E44 is added in batches, after the reaction is carried out for 1h, the temperature is heated to 100 ℃ for continuous reaction, the content of-NCO is measured by adopting a method of national standard HG/T2409-92, the reaction is complete when the content of-NCO is below 0.05 percent, the reaction is stopped, and the polyurethane prepolymer modified epoxy resin (UE) with more than 2 functional groups is obtained for standby.
And 3, step 3: the synthesis method of the high-strength and high-toughness vinyl ester resin comprises the following steps:
adding 816g of polyurethane prepolymer modified epoxy resin (UE) with more than 2 functional groups into a reaction bottle, stirring, heating to 80 ℃, dissolving 166.5g of methacrylic acid, 0.3g of catalyst benzyltrimethylammonium chloride and 1g of polymerization inhibitor hydroquinone and 2g of 2, 3-dichloro-1, 4-naphthoquinone, adding into a constant pressure dropping funnel, dropwise adding at the speed of 1d/s, slowly heating to 90 ℃ after dropwise adding, reacting at constant temperature until the acid value of the system is reduced to below 8mg/g KOH, cooling to below 80 ℃, adding 3.2g of solid paraffin and 655g of styrene monomer to ensure that the solid content of the resin is 60%, and uniformly stirring to finally obtain the high-strength vinyl ester toughened resin (VER) with more than 2 functional groups.
Example 2
The preparation method of the high-strength high-toughness vinyl ester resin comprises the following steps:
step 1: a polyurethane prepolymer synthesis step comprising:
200g of polyether glycol PPG1000 is added into a reaction bottle and stirred, nitrogen is introduced for protection, the reaction bottle is heated to 75 ℃, 71g of HDI is added into a constant-pressure dropping funnel and is dripped at the speed of 2d/s, after HDI is dripped, reaction is carried out at the constant temperature of 85 ℃, the content of-NCO is measured to be 6.88% by adopting a method of national standard HG/T2409-92, and the reaction is stopped when the theoretical value is reached, so that polyurethane Prepolymer (PUR) is obtained for later use.
Step 2: the synthesis method of the polyurethane prepolymer modified epoxy resin comprises the following steps:
adding 271g of polyurethane Prepolymer (PUR) into a reaction flask, stirring, introducing nitrogen for protection, heating the reaction flask to 95 ℃, adding 556g of epoxy resin E44 in batches, heating to 100 ℃ after reacting for 1 hour, continuing to react, measuring the-NCO content by adopting a national standard HG/T2409-92 method, stopping the reaction until the-NCO content is below 0.05%, and obtaining the polyurethane prepolymer modified epoxy resin (UE) with more than 2 functional groups for later use.
And step 3: the synthesis method of the high-strength and high-toughness vinyl ester resin comprises the following steps:
adding 827g of polyurethane prepolymer modified epoxy resin (UE) with more than 2 functional groups into a reaction bottle, stirring, heating to 80 ℃, then dissolving 200g of methacrylic acid, 0.4g of catalyst triphenylphosphine and 3g of polymerization inhibitor on hydroxy-benzoquinone, adding into a constant pressure dropping funnel, dropwise adding at a speed of 1d/s, slowly heating to 90 ℃ after dropwise adding is finished, reacting at constant temperature until the acid value of the system is reduced to below 8mg/gKOH, cooling to below 80 ℃, adding 3g of solid paraffin and 553g of styrene monomer to ensure that the solid content of the resin is 65%, and stirring uniformly to finally obtain the high-strength toughened Vinyl Ester Resin (VER) with more than 2 functional groups.
Comparative example 1
Adding 500g of epoxy resin (E44) into a reaction bottle, stirring, heating to 80 ℃, then dissolving 180g of methacrylic acid, 0.3g of catalyst benzyltrimethylammonium chloride and 1g of polymerization inhibitor hydroquinone and 2g of 2, 3-dichloro-1, 4-naphthoquinone, then adding into a constant pressure dropping funnel, dropwise adding at the speed of 1d/s, slowly heating to 90 ℃ after dropwise adding, reacting at constant temperature until the acid value of the system is reduced to below 8mg/gKOH, cooling to below 80 ℃, adding 2.2g of solid paraffin and 453g of styrene monomer to ensure that the solid content of the resin is 60%, stirring uniformly, and finally obtaining the non-toughened Vinyl Ester Resin (VER).
Comparative example 2
The method for grafting and modifying the epoxy vinyl ester resin by the polyurethane prepolymer comprises the following steps:
step 1: a polyurethane prepolymer synthesis step comprising:
adding 300g of polyether glycol PPG2000 into a reaction bottle, stirring, introducing nitrogen for protection, heating the reaction bottle to 80 ℃, then adding 54.6g of TDI into a constant-pressure dropping funnel, dropwise adding at the speed of 2d/s, reacting at the constant temperature of 90 ℃ after the TDI is dropwise added, measuring the-NCO content to be 3.88% by adopting a method of national standard HG/T2409-92, stopping the reaction when the theoretical value is reached, and obtaining a polyurethane Prepolymer (PUR) for later use.
Step 2: the method comprises the following steps of synthesizing an epoxy vinyl ester resin:
adding 309g of epoxy resin E51 (subjected to dehydration treatment) into a reaction bottle, stirring, heating the reaction bottle to 95 ℃, dissolving 129g of methacrylic acid, 1.5g of catalyst benzyldimethylamine and 0.15g of polymerization inhibitor hydroquinone, adding into a constant-pressure dropping funnel, dropwise adding at the speed of 2d/s, slowly heating to 105 ℃ after dropwise adding, reacting at constant temperature until the acid value of the system is reduced to below 8mg/g KOH to obtain epoxy vinyl ester resin (VE), and cooling to below 60 ℃ for later use.
And step 3: the synthesis of the polyurethane prepolymer grafted modified epoxy vinyl ester resin comprises the following steps:
adding 52.56g (12% of epoxy vinyl ester mass fraction) of the polyurethane prepolymer obtained in the step 1 and 1g of dibutyltin laurate serving as a catalyst into the reaction bottle in the step 2, stirring, introducing nitrogen for protection, reacting at a constant temperature of 60 ℃, determining the-NCO content by adopting a method of national standard HG/T2409-92, stopping the reaction when the-NCO content is below 0.05%, adding 1g of solid paraffin and 329g of styrene monomer to enable the solid content of the resin to be 60%, and uniformly stirring to finally obtain the polyurethane prepolymer grafted modified epoxy Vinyl Ester Resin (VER).
When the urethane prepolymer is added in an amount of 20% by mass of the epoxy vinyl ester, the reaction is extremely unstable and the gel phenomenon is liable to occur.
The results of the performance tests of the products obtained in the above examples and comparative examples are shown in table 1 below:
table 1 shows the results of the performance tests on the prepared Vinyl Ester Resin (VER)
The test result shows that after the high-strength high-toughness vinyl ester resin prepared by modification is cured, the volume shrinkage rate of a resin casting body is obviously reduced, the toughness is obviously improved, the elongation at break is more than 12%, the impact strength is good, the bonding performance and the strength are also improved to a certain extent, the comprehensive performance is good, and the product is stable.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention, and all modifications, equivalents, improvements and the like made within the spirit and technical scope of the present invention are within the scope of the present invention.
Claims (8)
1. A preparation method of a high-strength high-toughness vinyl ester resin is characterized by comprising the following steps:
step 1: a polyurethane prepolymer synthesis step comprising:
adding polyether glycol into a reaction bottle, stirring, introducing nitrogen for protection, heating the reaction bottle to 70-90 ℃, adding diisocyanate into a constant-pressure dropping funnel, dropping at the speed of 1-3 d/s, reacting at the constant temperature of 80-100 ℃ after the diisocyanate is dropped, measuring the content of-NCO, and stopping the reaction when a theoretical value is reached to obtain a polyurethane prepolymer for later use;
and 2, step: the synthesis method of the polyurethane prepolymer modified epoxy resin comprises the following steps:
adding the polyurethane Prepolymer (PUR) into a reaction bottle, stirring, introducing nitrogen for protection, heating the reaction bottle to 80-90 ℃, adding the epoxy resin in batches, heating to 90-110 ℃ for continuous reaction after reacting for 0.5-1h,
when the-NCO content is 0 to 0.05 percent, namely the reaction is complete, stopping the reaction to obtain polyurethane prepolymer modified epoxy resin (UE) for later use;
and step 3: vinyl ester resin synthesis step, comprising:
adding the polyurethane prepolymer modified epoxy resin (UE) into a reaction bottle, stirring, heating to 75-85 ℃, dissolving unsaturated monocarboxylic acid, a catalyst and a polymerization inhibitor, adding into a constant-pressure dropping funnel, dropwise adding at a speed of 1-2d/s, slowly heating to 90-100 ℃, reacting at a constant temperature until the acid value of the system is reduced to below 8mg/gKOH, cooling to below 80 ℃, adding 0.1-0.2% of solid paraffin and 30-40% of styrene monomer to ensure that the solid content of the resin is 60-70%, and stirring uniformly to finally obtain the high-strength high-toughness vinyl ester resin;
the catalyst is one or more of benzyl dimethylamine, benzyl trimethyl ammonium chloride, benzyl triethyl ammonium chloride, triphenylphosphine and triphenyl phosphine chloride.
2. The preparation method according to claim 1, wherein the polyether diol is one or more of polyoxypropylene diol PPG600, PPG1000 and PPG 2000.
3. The production method according to claim 1, wherein the polyether glycol is dehydrated in advance.
4. The method according to claim 1, wherein the diisocyanate is one or more selected from the group consisting of toluene diisocyanate, diphenylmethane-4, 4' -diisocyanate, hexamethylene 1, 6-diisocyanate, isophorone diisocyanate, and xylylene diisocyanate.
5. The method according to claim 1, wherein the epoxy resin is one or more of E54, E51, E44 and E42.
6. The method according to claim 1, wherein the epoxy resin is dehydrated in advance.
7. The method according to claim 1, wherein the unsaturated monocarboxylic acid is one or a combination of acrylic acid and methacrylic acid.
8. The method according to claim 1, wherein the polymerization inhibitor is one or more selected from hydroquinone, p-tert-butylcatechol, 2, 6-di-tert-butyl-p-methylphenol, p-benzoquinone, p-hydroxy-hemibenzoquinone, and 2, 3-dichloro-1, 4-naphthoquinone.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102604528A (en) * | 2012-03-09 | 2012-07-25 | 常熟市协新冶金材料有限公司 | Epoxy acrylic ester modified water-based polyurethane coating |
| CN110776644A (en) * | 2019-11-29 | 2020-02-11 | 华东理工大学 | Toughened modified vinyl ester resin and synthetic method thereof |
| CN111171282A (en) * | 2020-01-22 | 2020-05-19 | 黎明化工研究设计院有限责任公司 | Method for synthesizing polyurethane-epoxy acrylate |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102604528A (en) * | 2012-03-09 | 2012-07-25 | 常熟市协新冶金材料有限公司 | Epoxy acrylic ester modified water-based polyurethane coating |
| CN110776644A (en) * | 2019-11-29 | 2020-02-11 | 华东理工大学 | Toughened modified vinyl ester resin and synthetic method thereof |
| CN111171282A (en) * | 2020-01-22 | 2020-05-19 | 黎明化工研究设计院有限责任公司 | Method for synthesizing polyurethane-epoxy acrylate |
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