Epoxy toughening compatilizer and preparation method thereof

Abstract

The invention discloses an epoxy toughening compatilizer and a preparation method thereof, and relates to a compatilizer and a preparation method thereof. The invention aims to solve the problems that the material performance cannot be improved after the two materials are mixed due to large property difference and poor compatibility of the elastomer material and the epoxy resin, the toughening effect of the epoxy resin can be realized only by high addition proportion of the elastomer, but the rigidity of the epoxy resin is sacrificed. The compatilizer comprises an epoxy toughening compatilizer which comprises glycidyl acrylate, alkane acrylate, alkane olefin, an initiator and a molecular weight regulator. The invention belongs to the technical field of epoxy resin preparation.

Description

Technical Field

[0001] The invention relates to a compatibilizer and a preparation method thereof, belonging to the technical field of epoxy resin preparation. Background Art

[0002] Epoxy resin is one of the most widely used thermosetting resins. It has the advantages of excellent mechanical properties, thermal properties, high chemical stability, corrosion resistance, low shrinkage, easy processing and molding, and low cost. Epoxy resin has been widely used in structural materials as the matrix of fiber-reinforced composite materials; at the same time, due to its excellent bonding properties, wear resistance, and electrical insulation properties, it is widely used in aerospace, adhesives, electronics, coatings and other fields. However, pure epoxy resin has high cross-linking density and large internal stress after curing. It has the disadvantages of being brittle, easy to crack, poor impact resistance and poor heat resistance, and can no longer meet the requirements of these fields for high-performance materials. Therefore, the modification and toughening of epoxy resin has always been a hot topic of research at home and abroad. According to existing literature reports and practical experience, there are four methods for toughening epoxy resin:

[0003] 1. Use a second phase such as elastomer, thermoplastic resin or rigid particles to toughen and modify;

[0004] 2. Use thermoplastic resin to continuously penetrate the thermosetting resin to form an interpenetrating network for toughening and modification;

[0005] 3. Toughening by changing the chemical structure of the cross-linked network to increase the activity of the network chain molecules;

[0006] 4. Control the heterogeneity of the molecular cross-linking state to form a non-uniform structure that is conducive to plastic deformation to achieve toughening.

[0007] Among them, elastomer is a tough material with excellent toughness, and it has excellent toughening effect on many olefin materials. In terms of complementary material properties, elastomer materials and epoxy resins have their own advantages in performance, and the performance of materials can be upgraded and improved through performance complementarity. However, due to the large difference in the properties of elastomer materials and epoxy resins, the poor compatibility leads to the failure to improve the material performance after the two materials are mixed. It is often necessary to add a high proportion of elastomer to achieve the toughening effect of epoxy resin, but it will sacrifice the rigidity of epoxy resin, such as elastic modulus and strength. Summary of the invention

[0008] The present invention aims to solve the problem that due to the large difference in properties of elastomer materials and epoxy resins and the poor compatibility of the two materials, the material performance cannot be improved after the two materials are mixed, and a high proportion of elastomer addition is often required to achieve the toughening effect of the epoxy resin, but the rigidity of the epoxy resin will be sacrificed. Further, an epoxy toughening compatibilizer and a preparation method thereof are proposed.

[0009] The technical solution adopted by the present invention to solve the above problems is: the epoxy toughening compatibilizer of the present invention comprises glycidyl acrylate, alkyl acrylate, alkane olefin, initiator and molecular weight regulator.

[0010] Furthermore, the percentage of each component is: 25-40wt% of glycidyl acrylate, 25-40wt% of alkyl acrylate, 20-50wt% of alkane olefin, 0.5wt%-5wt% of initiator, and 0.01wt%-0.1wt% of molecular weight regulator.

[0011] Furthermore, the glycidyl acrylates are composed of one or both of glycidyl acrylate and glycidyl methacrylate.

[0012] Furthermore, the alkyl acrylates are composed of one or more of methyl methacrylate, isobornyl methacrylate, butyl acrylate, butyl methacrylate, isooctyl acrylate, isooctyl methacrylate, lauric acrylate, lauric methacrylate, octadecyl acrylate, octadecyl methacrylate, and the like.

[0013] Furthermore, the alkane olefin is composed of one or more of 1-octene, 1-dodecene, 1-tetradecene and 1-octadecene.

[0014] Furthermore, the initiator is composed of one or more of azobisisobutyronitrile, 2,4,6-(trimethylbenzoyl)diphenylphosphine oxide, ethyl 2,4,6-trimethylbenzoylphosphonate, 2-methyl-1-[4-methylthiophenyl]-2-morpholinyl-1-propanone, 2-isopropylthioxanthone, and ethyl 4-dimethylaminobenzoate.

[0015] Furthermore, the molecular weight regulator is composed of one or more of dodecyl mercaptan, n-docosyl mercaptan, dimethyl sulfide, dimethyl disulfide, and diphenyl sulfide.

[0016] The steps of the preparation method of the present invention include:

[0017] Step 1, weigh glycidyl acrylate monomer, alkyl acrylate monomer, and alkene monomer into a beaker, stir well, and then divide into two parts;

[0018] Step 2, adding a certain amount of molecular weight regulator to a portion of the mixed monomers in step 1 and placing the mixture in a flask and heating it in a water bath at 40° C., and turning on the ultraviolet light generator for irradiation;

[0019] Step 3, place another portion of the mixed monomers in step 1 in a light-proof flask, add the initiator, and after fully dissolving and mixing, add the mixture dropwise into the flask using a light-proof constant pressure funnel for reaction;

[0020] Step 4: After reacting for 4 to 5 hours, a viscous liquid product is obtained.

[0021] The beneficial effects of the present invention are as follows: the present invention improves the compatibility between the epoxy resin and the toughening material, reduces the addition ratio of the elastomeric material, takes into account the performance of the epoxy resin, and obtains a material system with balanced comprehensive performance. Example

[0022] Example 1

[0023] Step 1, respectively weigh 25g of glycidyl acrylate, 10g of methyl methacrylate, 10g of butyl acrylate, 5g of isobornyl methacrylate, 25g of 1-octene and 25g of octadecene in a beaker, stir well and divide into two portions of 60g and 40g;

[0024] Step 2, add 0.01 g of molecular weight regulator dodecyl mercaptan to 60 g of the mixed monomer in a, place the mixture in a flask, heat it in a 40° C. water bath, and turn on the ultraviolet light generator for irradiation;

[0025] Step 3, place 40g of the mixed monomers in a in a light-proof flask, add 0.5g of initiator AIBN and 2g of TPO, and after fully dissolving and mixing, drip into the flask using a light-proof constant pressure funnel for 1h;

[0026] Step 4: After maintaining light and temperature reaction for 4 to 5 hours, a viscous liquid product is obtained.

[0027] Example 2

[0028] Step 1, weigh 20g of glycidyl methacrylate, 10g of glycidyl acrylate, 15g of methyl methacrylate, 5g of butyl acrylate, 15g of butyl methacrylate, 20g of 1-dodecene and 15g of 1-tetradecene as alkane olefin monomers in a beaker, stir well and divide into two portions of 60g and 40g;

[0029] Step 2, add 0.03 g of molecular weight regulator n-docosyl mercaptan to 60 g of the mixed monomer in a, place the mixture in a flask, heat it in a 40° C. water bath, and turn on the ultraviolet light generator for irradiation;

[0030] Step 3, place 40g of the mixed monomers in a in a light-proof flask, add initiator TPO 1g, 907 3g, ITX 1g, fully dissolve and mix, and then drip into the flask using a light-proof constant pressure funnel for 1h;

[0031] Step 4: After maintaining light and temperature reaction for 4 to 5 hours, a viscous liquid product is obtained.

[0032] Example 3

[0033] Step 1, weigh 20g of glycidyl methacrylate, 10g of glycidyl acrylate, 10g of methyl methacrylate, 10g of lauryl acrylate, 15g of isooctyl methacrylate, 25g of alkane olefin monomer 1-dodecene, and 10g of 1-octadecene respectively into a beaker, stir well, and then divide into two portions of 60g and 40g;

[0034] Step 2, add 0.01 g of n-docosyl mercaptan and 0.02 g of dimethyl sulfide to 60 g of the mixed monomer in a, place the mixture in a flask, heat it in a 40° C. water bath, and turn on the ultraviolet light generator for irradiation;

[0035] Step 3, place 40g of the mixed monomers in a in a light-proof flask, add initiator EDB 1g, 907 3g, AIBN 1g, fully dissolve and mix, and then drip into the flask using a light-proof constant pressure funnel for 1h;

[0036] Step 4: After maintaining light and temperature reaction for 4 to 5 hours, a viscous liquid product is obtained.

[0037] Example 4

[0038] Step 1, weigh 15g of glycidyl methacrylate, 25g of glycidyl acrylate, 10g of methyl methacrylate, 10g of lauryl methacrylate, 20g of octadecyl methacrylate, 15g of 1-octene and 5g of 1-octadecene respectively into a beaker, stir well and divide into two portions of 60g and 40g;

[0039] Step 2: Add 0.02 g of diphenyl sulfide, 0.03 g of dimethyl sulfide and 0.03 g of n-docosyl mercaptan to 60 g of the mixed monomer in a, place the mixture in a flask, heat it in a water bath at 40° C., and turn on the ultraviolet light generator for irradiation;

[0040] Step 3, place 40g of the mixed monomers in a into a light-proof flask, add 2g of initiator TPO-L and 1g of AIBN, and after fully dissolving and mixing, drip into the flask using a light-proof constant pressure funnel for 1h;

[0041] Step 4: After maintaining light and temperature reaction for 4 to 5 hours, a viscous liquid product is obtained.

[0042] Example 5

[0043] Step 1, respectively weigh 5g of glycidyl methacrylate, 30g of glycidyl acrylate, 20g of isooctyl methacrylate, 10g of isobornyl methacrylate, 10g of butyl methacrylate, 10g of alkane olefin monomers 1-octene, 10g of 1-tetradecene, and 5g of 1-octadecene into a beaker, stir well, and then divide into two portions of 60g and 40g;

[0044] Step 2: Add 0.01 g of dodecyl mercaptan, 0.05 g of dimethyl disulfide and 0.04 g of diphenyl sulfide to 60 g of the mixed monomer in a, place the mixture in a flask, heat it in a 40° C. water bath, and turn on the ultraviolet light generator for irradiation;

[0045] Step 3, place 40g of the mixed monomers in a in a light-proof flask, add 2g of initiator TPO-L, 1g of AIBN and 1g of ITX, and after fully dissolving and mixing, drip into the flask using a light-proof constant pressure funnel for 1h;

[0046] Step 4: After maintaining light and temperature reaction for 4 to 5 hours, a viscous liquid product is obtained.

[0047] Example 6

[0048] Step 1, respectively weigh 30g of glycidyl acrylate, 10g of isooctyl methacrylate, 20g of isobornyl methacrylate, 5g of butyl methacrylate, 10g of 1-octene, 10g of 1-dodecene, 10g of 1-tetradecene and 5g of 1-octadecene in a beaker, stir well and divide into two portions of 60g and 40g;

[0049] Step 2, add 0.05 g of dodecyl mercaptan to 60 g of the mixed monomer in a and place in a flask and heat in a 40° C. water bath, and turn on the ultraviolet light generator for irradiation;

[0050] Step 3, place 40g of the mixed monomers in a into a light-proof flask, add 2g of initiator TPO-L and 2g of ITX, and after fully dissolving and mixing, drip into the flask using a light-proof constant pressure funnel for 1h;

[0051] Step 4: After maintaining light and temperature reaction for 4 to 5 hours, a viscous liquid product is obtained.

[0052] Example 7

[0053] Step 1, weigh 8g of glycidyl methacrylate, 22g of glycidyl acrylate, 16g of lauric methacrylate, 18g of isobornyl methacrylate, 6g of butyl methacrylate, 6g of alkane olefin monomers 1-octene, 12g of 1-tetradecene, and 12g of 1-octadecene in a beaker, stir well, and then divide into two portions of 60g and 40g;

[0054] Step 2, add 0.05 g of dodecyl mercaptan and 0.03 g of dimethyl disulfide to 60 g of the mixed monomer in a, place the mixture in a flask, heat it in a 40° C. water bath, and turn on the ultraviolet light generator for irradiation;

[0055] Step 3, place 40g of the mixed monomers in a in a light-proof flask, add 2g of initiator TPO-L, 1g of AIBN, and 2g of ITX, and after fully dissolving and mixing, drip into the flask using a light-proof constant pressure funnel for 1h;

[0056] Step 4: After maintaining light and temperature reaction for 4 to 5 hours, a viscous liquid product is obtained.

[0057] Example 8

[0058] Step 1, weigh 25 g of glycidyl methacrylate, 13 g of octadecyl methacrylate, 21 g of isobornyl methacrylate, 1 g of butyl methacrylate, 6 g of 1-octene, 10 g of 1-dodecene, 10 g of 1-tetradecene, and 14 g of 1-octadecene respectively in a beaker, stir well, and divide into two portions of 60 g and 40 g;

[0059] Step 2, add 0.03 g of dimethyl disulfide and 0.03 g of diphenyl sulfide to 60 g of the mixed monomer in a, place the mixture in a flask, heat it in a 40° C. water bath, and turn on the ultraviolet light generator for irradiation;

[0060] Step 3, place 40g of the mixed monomers in a in a light-proof flask, add initiator EDB 2g, AIBN 0.5g, ITX2.5g, fully dissolve and mix, and then drip into the flask using a light-proof constant pressure funnel for 1h;

[0061] Step 4: After maintaining light and temperature reaction for 4 to 5 hours, a viscous liquid product is obtained.

[0062] The above is only a preferred embodiment of the present invention and does not limit the present invention in any form. Although the present invention has been disclosed as a preferred embodiment as above, it is not used to limit the present invention. Any technician familiar with this profession can make some changes or modify the technical contents disclosed above into equivalent embodiments without departing from the scope of the technical solution of the present invention. However, any simple modification, equivalent replacement and improvement made to the above embodiments without departing from the content of the technical solution of the present invention, based on the technical essence of the present invention, within the spirit and principles of the present invention, still fall within the protection scope of the technical solution of the present invention.

Claims

1. An epoxy toughening compatibilizer, characterized in that: The invention comprises glycidyl acrylates, alkyl acrylates, alkane olefins, initiators and molecular weight regulators.

2. An epoxy toughening compatibilizer according to claim 1, characterized in that: The percentage of each component is: 25-40wt% of glycidyl acrylate, 25-40wt% of alkyl acrylate, 20-50wt% of alkane, 0.5wt%-5wt% of initiator, and 0.01wt%-0.1wt% of molecular weight regulator.

3. An epoxy toughening compatibilizer according to claim 1, characterized in that: Glycidyl acrylates are composed of one or both of glycidyl acrylate and glycidyl methacrylate.

4. The epoxy toughening compatibilizer according to claim 1, characterized in that: The alkyl acrylates are composed of one or more of methyl methacrylate, isobornyl methacrylate, butyl acrylate, butyl methacrylate, isooctyl acrylate, isooctyl methacrylate, lauric acrylate, lauric methacrylate, octadecyl acrylate, octadecyl methacrylate and the like.

5. The epoxy toughening compatibilizer according to claim 1, characterized in that: The alkane olefins are composed of one or more of 1-octene, 1-dodecene, 1-tetradecene and 1-octadecene.

6. The epoxy toughening compatibilizer according to claim 1, characterized in that: The initiator is composed of one or more of azobisisobutyronitrile, 2,4,6-(trimethylbenzoyl)diphenylphosphine oxide, 2,4,6-trimethylbenzoylphosphonic acid ethyl ester, 2-methyl-1-[4-methylthiophenyl]-2-morpholinyl-1-propanone, 2-isopropylthioxanthone, and 4-dimethylamino-benzoic acid ethyl ester.

7. The epoxy toughening compatibilizer according to claim 1, characterized in that: The molecular weight regulator is composed of one or more of dodecyl mercaptan, n-docosyl mercaptan, dimethyl sulfide, dimethyl disulfide, and diphenyl sulfide.

8. A method for preparing an epoxy toughening compatibilizer, characterized in that: The specific steps include: Step 1, weigh glycidyl acrylate monomer, alkyl acrylate monomer, and alkene monomer into a beaker, stir well, and then divide into two parts; Step 2, adding a certain amount of molecular weight regulator to a portion of the mixed monomers in step 1 and placing the mixture in a flask and heating it in a water bath at 40° C., and turning on the ultraviolet light generator for irradiation; Step 3, place another portion of the mixed monomers in step 1 in a light-proof flask, add the initiator, and after fully dissolving and mixing, add the mixture dropwise into the flask using a light-proof constant pressure funnel for reaction; Step 4: After reacting for 4 to 5 hours, a viscous liquid product is obtained.