A thickening type vinyl resin and a method for synthesizing the same

Abstract

The application belongs to the technical field of C08F, and more particularly relates to a thickening type vinyl resin and a synthesis method thereof. The thickening type vinyl resin is prepared from raw materials including a polyhydroxy resin and a vinyl resin, and the weight ratio of the polyhydroxy resin to the vinyl resin is 1:50-50:1. The thickening type vinyl resin prepared by the application can be thickened by isocyanate alone or thickened by isocyanate after being compounded with other vinyl ester resins. The new product prepared without changing the synthesis process of the original vinyl ester resin has very high economic benefits and market value.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of C08F, and more particularly relates to a thickening type vinyl resin and a synthesis method thereof. BACKGROUND

[0002] The thickening type resin is a basic condition necessary in the mold pressing process. The commonly used thickening type resin such as the vinyl resin has a long thickening time, which limits the application value. In order to further optimize the application of the vinyl resin in the mold pressing process, it is a relatively important challenge to adjust the thickening effect of the vinyl resin at the present stage.

[0003] Chinese patent CN109535349A discloses a multi-hydroxyl vinyl resin, a preparation method and a thickening method thereof. In the disclosed patent, the purpose of multi-hydroxyl is achieved through the reaction between the epoxy resin and the methacrylic acid, and the purpose of thickening is achieved. However, in the disclosed patent, the type of epoxy compound leads to the fact that the number of hydroxyl groups in the system during the preparation of the multi-hydroxyl vinyl resin cannot be accurately controlled, resulting in unstable thickening effect. On the other hand, in the disclosed patent, the multi-hydroxyl vinyl resin is prepared by one-pot method. The hydroxyl value content of the vinyl resin prepared under this process condition is not easy to control, and the use effect cannot be controlled by adjusting the hydroxyl value during the subsequent mold pressing process.

[0004] In order to further ensure the controllable quality of the prepared vinyl resin and reduce the difficulty in the preparation process, it is an important challenge for researchers at the present stage to optimize the preparation raw materials and synthesis method of the existing vinyl resin. SUMMARY

[0005] In order to solve the above technical problems, the first aspect of the present application provides a thickening type vinyl resin, and the preparation raw materials comprise: a multi-hydroxyl resin and a vinyl resin.

[0006] The weight ratio of the multi-hydroxyl resin and the vinyl resin is 1:50-50:1.

[0007] In some preferred embodiments, the preparation raw materials of the multi-hydroxyl resin at least comprise: active ingredients and acrylic acid and its derivatives; the active ingredients comprise glycidyl ether with epoxy group ≥3 and / or glycidyl ester with epoxy group ≥3.

[0008] In some preferred embodiments, the preparation raw materials of the vinyl resin at least comprise: epoxy resin, phenolic hydroxyl compound and alkenyl compound.

[0009] Further preferably, the phenolic hydroxyl compound is selected from bisphenol A.

[0010] Further preferably, the alkenyl-containing compound comprises an acrylate.

[0011] In some preferred embodiments, the acrylic acid and derivatives thereof are selected from at least one of methacrylic acid, acrylic acid, methyl methacrylate.

[0012] Further preferably, the acrylic acid and derivatives thereof are methacrylic acid.

[0013] Further preferably, the molar ratio of the active ingredient to the acrylic acid and derivatives thereof is 1:3-1:6.

[0014] In some preferred embodiments, the active ingredient is selected from at least one of trimethylol tri-glycidyl ether, glycerol tri-glycidyl ether, pentaerythritol glycidyl ether, sorbitol glycidyl ether, isocyanuric acid tri-glycidyl ester.

[0015] During the experiments, the applicant found through a large number of creative experiments that the addition of the active ingredient and the methacrylic acid in the system not only ensures that a certain number of active groups can be obtained in the prepared polyhydroxy resin system, but also ensures better controllability of the synthesis process and avoids the occurrence of explosive polymerization during the reaction. The reason for this phenomenon is that, with the addition of the active ingredient, when the molar ratio of the active ingredient to the acrylic acid and derivatives thereof is 1:3-1:6, a certain number of active epoxy groups exist in the system, and further esterification reactions can occur between the epoxy groups and the methacrylic acid through ring-opening reactions of the epoxy groups, which not only controls the hydroxyl value content in the system, but also ensures that more macromolecular substances exist in the prepared polyhydroxy resin, thereby ensuring the thickening effect when subsequently mixed with the vinyl resin.

[0016] In some preferred embodiments, the viscosity of the epoxy resin is 8000-24000 mPa·s at 25℃; preferably, the viscosity of the epoxy resin is 11000-14000 mPa·s at 25℃.

[0017] In some preferred embodiments, the raw materials for preparing the polyhydroxy resin and the vinyl resin further comprise a polymerization inhibitor.

[0018] In some preferred embodiments, the polymerization inhibitor is selected from at least one of hydroquinone, methylhydroquinone, and p-tert-butyl hydroquinone.

[0019] Further preferably, the polymerization inhibitor is methylhydroquinone.

[0020] In some preferred embodiments, the raw materials for preparing the polyhydroxy resin and the vinyl resin further comprise a catalyst.

[0021] Further preferably, the catalyst is a tertiary amine catalyst; more preferably, the tertiary amine catalyst is N, N-dimethylbenzylamine.

[0022] In some preferred embodiments, the raw materials for preparing the polyhydroxy resin further include styrene.

[0023] In some preferred embodiments, the raw materials for preparing the polyhydroxy resin include, by weight: active ingredient 5-20 parts, acrylic acid and its derivatives 15-20 parts, styrene 25-35 parts, polymerization inhibitor 0.05-0.25 parts, and catalyst 0.1-1 part.

[0024] In some preferred embodiments, the raw materials for preparing the polyhydroxy resin include, by weight: active ingredient 5-20 parts, acrylic acid and its derivatives 15-20 parts, styrene 25-35 parts, polymerization inhibitor 0.05-0.25 parts, and catalyst 0.1-1 part.

[0025] The second aspect of the present application provides a method for synthesizing a thickening-type vinyl resin, comprising the following steps:

[0026] 1. Synthesis of the polyhydroxy resin:

[0027] 1) Calculate the weight of each raw material in the formula, put the active ingredient into the reaction kettle, heat to 60-90℃, add the catalyst, and drop the acrylic acid and its derivatives into the kettle in a dropwise manner, control the reaction temperature at 85-95℃, drop for 40-90min, and keep warm after the end;

[0028] 2) Control the temperature at 95-105℃, and measure the acid value of the resin in the reaction kettle 1h / once after keeping warm; when the acid value is <4mgKOH / g, stop keeping warm;

[0029] 3) Cool to below 90℃, add the polymerization inhibitor and styrene, continue to stir for 10-50min, and filter when the temperature in the reaction kettle is <50℃, to obtain the polyhydroxy resin;

[0030] 2. Synthesis of the vinyl resin:

[0031] 1) Calculate the weight of each raw material in the formula, put the epoxy resin into the reaction kettle, heat to 85-125℃, then add the catalyst and the phenolic hydroxyl compound, heat to 120-180℃ and keep warm, measure the epoxy equivalent weight of the resin in the reaction kettle 1h / once after keeping warm, and immediately cool to 104℃ when the epoxy equivalent weight of the resin reaches 330-340g / eq;

[0032] 2) Add a polymerization inhibitor, methacrylic acid to the reaction kettle, control the reaction temperature 100-110℃, measure the acid value and epoxy equivalent weight in the reaction kettle every 1h / time, when the acid value <4mgKOH / g, and the epoxy equivalent weight reaches the control index range, the heat preservation is ended, and immediately cooling down;

[0033] 3) Cool down to below 90℃, add a polymerization inhibitor, an alkenyl compound to carry out alkenylation, continue to stir for 30min, then filter when the temperature in the reaction kettle <50℃, to obtain a vinyl ester resin;

[0034] 3. Synthesis of thickening type vinyl resin:

[0035] Mix the polyhydroxy resin and the vinyl resin to obtain the thickening type vinyl ester resin.

[0036] During the experiment, the applicant optimizes the process of preparing the vinyl resin through a large number of creative experiments, and prepares the thickening type vinyl resin prepared by the three-step synthesis method. In the preparation process, the thickening effect of the prepared ethylene resin can be controlled by further controlling the hydroxyl value content of the polyhydroxy resin and the vinyl resin, and in the subsequent use process, especially in the mold forming process, the content of hydroxyl can be adjusted according to the actual needs, which ensures that the prepared polyhydroxy resin and the vinyl resin can be used in multiple situations by mixing in different proportions, thereby expanding its use value and application field.

[0037] Advantages: the thickening type vinyl resin prepared by the present application has the following advantages compared with the prior art:

[0038] 1. The synthesis process of the thickening type vinyl resin prepared by the present application has no by-products, and the raw material utilization rate is high;

[0039] 2. The polyhydroxy, low viscosity resin synthesized by the present application can effectively reduce the viscosity of the system after being compounded with the vinyl ester resin, so as to meet the process of SMC;

[0040] 3. The thickening type vinyl resin prepared by the present application can be thickened by isocyanate alone, or can be compounded with other vinyl ester resins and then thickened by isocyanate. The new product prepared under the premise of not changing the synthesis process of the original vinyl ester resin has very high economic benefit and market value. DETAILED DESCRIPTION

[0041] Example

[0042] Example 1

[0043] A thickening type vinyl resin, raw materials for preparing the same including a polyhydroxy resin and a vinyl resin, the weight ratio of the polyhydroxy resin and the vinyl resin being 2:3.

[0044] The raw materials for preparing the polyhydroxy resin include, by weight parts, an active ingredient 15 parts, acrylic acid and its derivatives 18 parts, styrene 30 parts, a polymerization inhibitor 0.1 part, and a catalyst 0.1 part.

[0045] The active ingredient is pentaerythritol glycidyl ether;

[0046] The acrylic acid and its derivatives are methacrylic acid;

[0047] The polymerization inhibitor is methylhydroquinone;

[0048] The catalyst is N, N-dimethylbenzylamine.

[0049] The raw materials for preparing the vinyl resin include, by weight parts, an epoxy resin 35 parts, a phenolic hydroxyl compound 20 parts, a catalyst 0.1 part, acrylic acid and its derivatives 10 parts, an alkenyl-containing compound 30 parts, and a polymerization inhibitor 0.1 part.

[0050] The epoxy resin has a viscosity of 11000-14000 mPa·s at 25℃, and is a product available from

[0051] The phenolic hydroxyl compound is bisphenol A;

[0052] The polymerization inhibitor is methylhydroquinone;

[0053] The catalyst is N, N-dimethylbenzylamine.

[0054] The acrylic acid and its derivatives are methacrylic acid;

[0055] The alkenyl-containing compound is hydroxypropyl methacrylate.

[0056] A method for synthesizing a thickening type vinyl resin, comprising the following steps:

[0057] 1. Synthesis of a polyhydroxy resin:

[0058] 1) Calculate the weight of each raw material in the formula, put the active ingredient into the reaction kettle, heat to 80℃, add the catalyst, and drop the acrylic acid and its derivatives into the kettle in a dropwise manner, control the reaction temperature at 90±2℃, drop for 90min, and keep warm after the end;

[0059] 2) Control the temperature at 100℃, and measure the acid value of the resin in the reaction kettle every 1h after keeping warm; when the acid value is <4mgKOH / g, stop keeping warm;

[0060] 3) cooling to below 90℃, adding polymerization inhibitor and styrene, continuing to stir for 30 min, then filtering when the temperature in the reactor is <50℃, to obtain the polyhydroxy resin;

[0061] 2. Synthesis of the vinyl resin:

[0062] 1) calculating the weight of each raw material in the formula, putting the epoxy resin into the reactor, heating to 110℃, then adding the catalyst and the phenolic hydroxyl compound, heating to 160℃ and keeping the temperature, measuring the epoxy equivalent weight of the resin in the reactor every 1h, when the epoxy equivalent weight of the resin reaches 330-340g / eq, immediately cooling to 104℃;

[0063] 2) adding the polymerization inhibitor and the methacrylic acid into the reactor, controlling the reaction temperature at 108±2℃, measuring the acid value and the epoxy equivalent weight in the reactor every 1h, when the acid value is <4mgKOH / g and the epoxy equivalent weight reaches the controlled index range, ending the keeping temperature, and immediately cooling;

[0064] 3) cooling to below 90℃, adding the polymerization inhibitor and the alkenyl-containing compound to perform alkenylation, continuing to stir for 30 min, then filtering when the temperature in the reactor is <50℃, to obtain the vinyl ester resin;

[0065] 3. Synthesis of the thickening-type vinyl resin:

[0066] Mixing the polyhydroxy resin and the vinyl resin in a certain proportion to obtain the thickening-type vinyl ester resin.

[0067] Example 2

[0068] A thickening-type vinyl resin, the raw materials for preparing the same include a polyhydroxy resin and a vinyl resin, and the weight ratio of the polyhydroxy resin to the vinyl resin is 1.5:3.

[0069] The raw materials for preparing the polyhydroxy resin include, by weight: 15 parts of active ingredient, 18 parts of acrylic acid and its derivatives, 30 parts of styrene, 0.1 part of polymerization inhibitor, and 0.1 part of catalyst.

[0070] The active ingredient is trimethylol triepoxy ether;

[0071] The acrylic acid and its derivatives are methacrylic acid;

[0072] The polymerization inhibitor is methylhydroquinone;

[0073] The catalyst is N,N-dimethylbenzylamine.

[0074] The raw materials for preparing the vinyl resin include, by weight: 35 parts of epoxy resin, 20 parts of phenolic hydroxyl compound, 0.1 part of catalyst, 10 parts of acrylic acid and its derivatives, 30 parts of alkenyl-containing compound, and 0.1 part of polymerization inhibitor.

[0075] The epoxy resin has a viscosity of 11000-14000 mPa·s at 25℃ and is available from.

[0076] The phenolic hydroxyl compound is bisphenol A.

[0077] The polymerization inhibitor is methylhydroquinone.

[0078] The catalyst is N,N-dimethylbenzylamine.

[0079] The acrylic acid and its derivatives are methyl methacrylic acid.

[0080] The alkenyl-containing compound is hydroxypropyl methacrylate.

[0081] A method for synthesizing a thickening-type vinyl resin includes the following steps:

[0082] 1. Synthesis of polyhydroxy resin:

[0083] 1) Calculate the weight of each raw material in the formula, put the active ingredients into the reaction kettle, heat to 80℃, add catalyst, and drop the acrylic acid and its derivatives into the kettle in a dropwise manner, control the reaction temperature at 90±2℃, drop for 90min, and keep warm after the end;

[0084] 2) Keep the temperature at 100℃, and measure the acid value of the resin in the reaction kettle every 1h after keeping warm; when the acid value is <4mgKOH / g, stop keeping warm;

[0085] 3) Cool to below 90℃, add polymerization inhibitor and styrene, continue stirring for 30min, and filter when the temperature in the reaction kettle is <50℃, to obtain polyhydroxy resin;

[0086] 2. Synthesis of vinyl resin:

[0087] 1) Calculate the weight of each raw material in the formula, put the epoxy resin into the reaction kettle, heat to 110℃, then add catalyst and phenolic hydroxyl compound, heat to 160℃ and keep warm, measure the epoxy equivalent weight of the resin in the reaction kettle every 1h after keeping warm, and immediately cool to 104℃ when the epoxy equivalent weight of the resin reaches 330-340g / eq;

[0088] 2) Add polymerization inhibitor, methacrylic acid to the reactor, control the reaction temperature 108±2℃, every 1h / once determine the acid value and epoxy equivalent in the reactor, when the acid value <4mgKOH / g, epoxy equivalent reaches the control index range, the holding ends, immediately cooling;

[0089] 3) Cooling to 90℃ or less, adding polymerization inhibitor, ene containing compound to dilute ene, continue to stir for 30min, when the temperature in the reactor <50℃, filter, obtain the vinyl ester resin;

[0090] 3. Synthesis of thickening type vinyl resin:

[0091] Mix the polyhydroxy resin and the vinyl resin in proportion to obtain the thickening type vinyl ester resin.

[0092] Example 3

[0093] A thickening type vinyl resin, the specific embodiment is the same as example 1, and the difference from example 1 is that the molar ratio of active ingredients, acrylic acid and its derivatives is 1:8.

[0094] Example 4

[0095] A thickening type vinyl resin, the specific embodiment is the same as example 1, and the difference from example 1 is that the active ingredient is sorbitol glycidyl ether.

[0096] Example 5

[0097] A thickening type vinyl resin, the specific embodiment is the same as example 1, and the difference from example 1 is that the acrylic acid and its derivatives are selected from acrylic acid.

[0098] Example 6

[0099] A thickening type vinyl resin, the specific embodiment is the same as example 1, and the difference from example 1 is that the preparation method is:

[0100] 1) Add active ingredients, methacrylic acid, epoxy resin, bisphenol A, catalyst, polymerization inhibitor to the reaction container under nitrogen protection, then heat to 70℃ at a rate of 5℃ / min, control the heating rate, so that the system is heated to 90℃ within 105min, and keep warm for 180min;

[0101] 2) Add styrene to the product obtained in 1), continue to stir for 30min, and cool to room temperature.

[0102] Performance test:

[0103] The thickening type vinyl resin prepared above is subjected to the following performance test:

[0104] 1. Viscosity test:

[0105] 2. Heat deflection temperature test:

[0106] Experiments Viscosity / cp Heat deflection temperature / °C Example 1 750-900 105-109 Example 2 450-550 101-105 Example 3 230-300 65-73 Example 4 2200-2600 107-110 Example 5 350-500 99-102 Example 6 300-650 95-104

Claims

1. A thickening vinyl resin, characterized in that, The raw materials for preparation include: polyhydroxy resin and vinyl resin; The weight ratio of the polyhydroxy resin to the vinyl resin is 1:50 to 50:1; The raw materials for preparing the polyhydroxy resin include at least: an active ingredient and acrylic acid and its derivatives; the active ingredient includes glycidyl ethers with ≥3 epoxy groups and / or glycidyl esters with ≥3 epoxy groups; The raw materials for preparing the vinyl resin include at least: epoxy resin, phenolic hydroxyl compound, and alkenyl compound; The acrylic acid and its derivatives are selected from at least one of methacrylic acid, acrylic acid, and methyl methacrylate; The active ingredient is selected from at least one of trimethyloltriglycidyl ether, glycerol triglycidyl ether, pentaerythritol triglycidyl ether, sorbitol triglycidyl ether, and triglycidyl isocyanurate. The molar ratio of the active ingredient, acrylic acid and its derivatives is 1:3 to 1:

6.

2. The thickening vinyl resin according to claim 1, characterized in that, The epoxy resin has a viscosity of 8000-24000 mPa·s at 25℃.

3. The thickening vinyl resin according to claim 1, characterized in that, The epoxy resin has a viscosity of 11000-14000 mPa·s at 25℃.

4. The thickening vinyl resin according to any one of claims 1-3, characterized in that, The raw materials for preparing the polyhydroxy resin and vinyl resin also include polymerization inhibitors.

5. The thickening vinyl resin according to claim 4, characterized in that, The polymerization inhibitor is selected from at least one of hydroquinone, methylhydroquinone, and p-tert-butylcatechol.

6. A method for synthesizing a thickening vinyl resin according to any one of claims 4-5, characterized in that, Includes the following steps:

1. Synthesis of polyhydroxy resins: The raw materials for preparing the polyhydroxy resin, by weight, include: The active ingredient consists of 5-20 parts, acrylic acid and its derivatives of 15-20 parts, styrene of 25-35 parts, polymerization inhibitor of 0.05-0.25 parts, and catalyst of 0.1-1 parts. 1) Calculate the weight of each raw material in the formula, put the active ingredient into the reaction vessel, heat to 60-90℃, add acrylic acid and its derivatives into the vessel dropwise, control the reaction temperature at 85-95℃, and finish adding within 40-90 minutes. After the reaction is completed, keep the vessel at the temperature. 2) The holding temperature should be controlled at 95-105℃. After holding, the acid value of the resin in the reactor should be measured every 1 hour. When the acid value is <4mgKOH / g, the holding should be stopped. 3) Cool down to below 90℃, add polymerization inhibitor to dilute olefin, continue stirring for 10-50 minutes, and when the temperature in the reactor is <50℃, filter to obtain polyhydroxy resin; 2. Synthesis of vinyl resins: The raw materials for preparing the vinyl resin, by weight, include: 25-40 parts epoxy resin, 5-21 parts phenolic hydroxyl compound, 0.1-1 part catalyst, 5-15 parts acrylic acid and its derivatives, 25-35 parts alkenyl compound, and 0.05-0.25 parts polymerization inhibitor. 1) Calculate the weight of each raw material in the formula, put the epoxy resin into the reactor, heat it to 85-125℃, then add the phenolic hydroxyl compound, heat it to 120-180℃ and keep it at that temperature. After keeping it at that temperature, measure the epoxy equivalent of the resin in the reactor every 1 hour. When the epoxy equivalent of the resin reaches the controlled index range, immediately cool it down to 104℃. 2) Add polymerization inhibitor to the reactor, control the reaction temperature at 100-110℃, and measure the acid value and epoxy equivalent in the reactor every 1 hour. When the acid value is <4mgKOH / g and the epoxy equivalent reaches the controlled index range, the heat preservation ends and the temperature is immediately reduced. 3) Cool down to below 90℃, add polymerization inhibitor and alkenyl compound to dilute the olefin, continue stirring for 30 minutes, and when the temperature in the reactor is <50℃, filter to obtain vinyl ester resin; 3. Synthesis of thickening vinyl resins: By mixing polyhydroxy resin and vinyl resin, a thickening vinyl ester resin is obtained.