Preparation method of modified acrylic resin

Abstract

The invention relates to the technical field of acrylic resin modification, in particular to a preparation method of modified acrylic resin. The invention provides a preparation method of modified acrylic resin, which comprises the following steps: mixing an emulsifier, a modifier, a cross-linking agent, a polymeric monomer and a first initiator, and carrying out first copolymerization reaction to obtain a first copolymer; and mixing the first copolymer with a second initiator, and carrying out a second copolymerization reaction to obtain the modified acrylic resin. The cross-linking agent (AAEM) is added into a reaction system, so that the emulsifying effect of the emulsifying agent is improved, and the copolymerization effect among monomers is enhanced. In addition, according to the preparation method, after the first copolymerization reaction, the initiator is added again, and the second copolymerization reaction is added, so that the copolymerization effect and yield of the product are further enhanced.

Description

Technical Field

[0001] The invention relates to the technical field of acrylic resin modification, and in particular to a method for preparing modified acrylic resin. Background Art

[0002] Acrylic resin, as a coating film-forming substance, gives the paint film excellent mechanical properties, high gloss, high transparency and other excellent properties, but its paint film also has the disadvantages of low hardness, poor thermal and light stability, easy staining, and insufficient water resistance. The main chain of silicone polymer is Si-O bond with higher bond energy than CC, so it has excellent weather resistance, heat resistance, cold resistance and water resistance.

[0003] Therefore, the use of organosilicon to modify acrylic resin to obtain organosilicon-modified resin with the advantages of both has become a hot topic in recent years. However, in the process of modifying acrylic resin using organosilicon, the yield of the product (modified acrylic resin) is low. Summary of the invention

[0004] In order to solve the problems existing in the prior art, the present invention provides a method for preparing a modified acrylic resin. The preparation method provided by the present invention enhances the copolymerization effect and yield of the modified acrylic resin.

[0005] The present invention provides a method for preparing a modified acrylic resin, comprising the following steps:

[0006] An emulsifier, a modifier, a cross-linking agent, a polymerization monomer and a first initiator are mixed to carry out a first copolymerization reaction to obtain a first copolymer;

[0007] The first copolymer and the second initiator are mixed to carry out a second copolymerization reaction to obtain the modified acrylic resin; the crosslinking agent includes acetoacetoxyethyl methacrylate;

[0008] The polymerizable monomer includes at least one of a hard monomer, a soft monomer, a functional monomer or a water-soluble monomer; the hard monomer includes one or more of methyl acrylate, methyl methacrylate, ethyl acrylate and styrene;

[0009] The temperature of the first copolymerization reaction is 50-85°C; the temperature of the second copolymerization reaction is 60-85°C.

[0010] Preferably, the emulsifier includes one or more of K12 emulsifier, NP-10 emulsifier, EPA 1963 emulsifier, EPA 073 emulsifier, PF20S emulsifier, DSA502 emulsifier, Hostaphat 1308 emulsifier, CPA 100 emulsifier, CPA100 XS emulsifier, LCN118 emulsifier, LCN287 emulsifier, LCN407 emulsifier, UD 030 emulsifier, UD 050 emulsifier, UD110 emulsifier, X088 emulsifier, X307 emulsifier, X407 emulsifier, X1005 emulsifier, PF10 emulsifier, PF20 emulsifier, PF40 emulsifier, PF80 emulsifier, 2A1 emulsifier, A102 emulsifier and Cytec OT75 emulsifier.

[0011] Preferably, the modifier includes one or more of vegetable oleic acid, epoxy soybean oil, methylchlorosilane, phenylchlorosilane, methylvinylchlorosilane, ethyltrichlorosilane, propyltrichlorosilane, vinyltrichlorosilane, γ-chloropropyltrichlorosilane and fluorosilicon monomer.

[0012] Preferably, the water-soluble monomer comprises methylene succinic acid and / or acrylic acid.

[0013] Preferably, the soft monomer includes one or more of ethyl methacrylate, butyl acrylate, butyl methacrylate, isooctyl acrylate, isooctyl methacrylate and tert-butyl methacrylate.

[0014] Preferably, the functional monomer includes one or more of acrylamide, methacrylamide, N-hydroxymethyl acrylamide and N-hydroxyethyl acrylamide, glycidyl acrylate, glycidyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, lauryl acrylate, lauryl methacrylate, octadecyl acrylate, octadecyl methacrylate, cyclohexyl methacrylate, trifluoroethyl methacrylate, vinyl acetate, versatile vinyl carbonate, dicyclopentadienyl acrylate, dicyclopentadienyl methacrylate, isobornyl acrylate, isobornyl methacrylate, diallyl phthalate, allyl methacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, vinyl trimethoxysilane, vinyl triethoxysilane and γ-methacryloxypropyl trimethoxysilane.

[0015] Preferably, the first copolymerization reaction time is 0.1 to 0.3 h.

[0016] Preferably, the second copolymerization reaction time is 30 to 90 minutes.

[0017] The present invention provides a method for preparing a modified acrylic resin, comprising the following steps: mixing an emulsifier, a modifier, a cross-linking agent, a polymerizable monomer and a first initiator, performing a first copolymerization reaction, and obtaining a first copolymer; mixing the first copolymer and a second initiator, and performing a second copolymerization reaction, and obtaining the modified acrylic resin; the cross-linking agent comprises AAEM; the polymerizable monomer comprises at least one of a hard monomer, a soft monomer, a functional monomer or a water-soluble monomer; the hard monomer comprises one or more of methyl acrylate, methyl methacrylate, ethyl acrylate and styrene; the temperature of the first copolymerization reaction is 50 to 85° C.; the temperature of the second copolymerization reaction is 60 to 85° C. The present invention increases the stability and shear force of the resin by adding a cross-linking agent (AAEM) to the reaction system, and has good powder encapsulation, thereby enhancing the copolymerization effect between the monomers. In addition, the preparation method of the present invention adds an initiator again after the first copolymerization reaction, adds a second copolymerization reaction, and further enhances the copolymerization effect and yield of the product. DETAILED DESCRIPTION

[0018] The present invention provides a method for preparing a modified acrylic resin, comprising the following steps:

[0019] An emulsifier, a modifier, a cross-linking agent, a polymerization monomer and a first initiator are mixed to carry out a first copolymerization reaction to obtain a first copolymer;

[0020] The first copolymer and the second initiator are mixed to carry out a second copolymerization reaction to obtain the modified acrylic resin; the crosslinking agent includes acetoacetoxyethyl methacrylate (AAEM);

[0021] The polymerizable monomer includes at least one of a hard monomer, a soft monomer, a functional monomer or a water-soluble monomer; the hard monomer includes one or more of methyl acrylate, methyl methacrylate, ethyl acrylate and styrene;

[0022] The temperature of the first copolymerization reaction is 50-85°C; the temperature of the second copolymerization reaction is 60-85°C.

[0023] In the present invention, the emulsifier preferably includes K12 emulsifier, NP-10 emulsifier, EPA 1963 emulsifier, EPA073 emulsifier, PF20S emulsifier, DSA502 emulsifier, Hostaphat 1308 emulsifier, CPA 100 emulsifier, CPA100XS emulsifier, LCN118 emulsifier, LCN287 emulsifier, LCN407 emulsifier, UD 030 emulsifier, UD One or more of 050 emulsifier, UD110 emulsifier, X088 emulsifier, X307 emulsifier, X407 emulsifier, X1005 emulsifier, PF10 emulsifier, PF20 emulsifier, PF40 emulsifier, PF80 emulsifier, 2A1 emulsifier, A102 emulsifier and Cytec OT75 emulsifier, more preferably K12 emulsifier or NP-10 emulsifier.

[0024] In the present invention, the polymerizable monomer preferably includes at least one of a hard monomer, a soft monomer, a functional monomer or a water-soluble monomer.

[0025] In the present invention, the hard monomer includes one or more of methyl acrylate, methyl methacrylate, ethyl acrylate and styrene, preferably methyl acrylate or methyl methacrylate.

[0026] In the present invention, the soft monomer preferably includes one or more of ethyl methacrylate, butyl acrylate, butyl methacrylate, isooctyl acrylate, isooctyl methacrylate and tert-butyl methacrylate, and more preferably ethyl methacrylate or butyl acrylate.

[0027] In the present invention, the water-soluble monomer includes itaconic acid and / or acrylic acid, more preferably acrylic acid.

[0028] In the present invention, the functional monomer preferably includes one or more of acrylamide, methacrylamide, N-hydroxymethyl acrylamide and N-hydroxyethyl acrylamide, glycidyl acrylate, glycidyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, lauryl acrylate, lauryl methacrylate, octadecyl acrylate, octadecyl methacrylate, cyclohexyl methacrylate, trifluoroethyl methacrylate, vinyl acetate, vinyl versatate, dicyclopentadienyl acrylate, dicyclopentadienyl methacrylate, isobornyl acrylate, isobornyl methacrylate, diallyl phthalate, allyl methacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, vinyl trimethoxysilane, vinyl triethoxysilane and γ-methacryloxypropyl trimethoxysilane, more preferably acrylamide or methacrylamide.

[0029] In the present invention, the modifier preferably includes one or more of vegetable oil acid, epoxy soybean oil, methylchlorosilane, phenylchlorosilane, methylvinylchlorosilane, ethyltrichlorosilane, propyltrichlorosilane, vinyltrichlorosilane, γ-chloropropyltrichlorosilane and fluorosilicon monomer, more preferably methylvinylchlorosilane, ethyltrichlorosilane or propyltrichlorosilane.

[0030] In the present invention, the cross-linking agent includes AAEM.

[0031] In the present invention, the first initiator preferably includes one or more of ammonium persulfate, sodium bisulfite, sodium dihydrogen phosphate, sodium tripolyphosphate, sodium persulfate, potassium persulfate and hydrogen peroxide, and more preferably ammonium persulfate and hydrogen peroxide.

[0032] In the present invention, the mass ratio of the modifier, the crosslinking agent and the polymerized monomer is preferably 2:3:100. In the present invention, the mass ratio of the polymerized monomer and the emulsifier is preferably 100:5. In the present invention, the mass ratio of the polymerized monomer and the first initiator is preferably 100:0.02.

[0033] In the present invention, the mixing method is preferably stirring, the stirring speed is preferably 10 to 25 rpm, more preferably 20 rpm, and the stirring time is preferably 30 to 60 min, more preferably 50 min.

[0034] In the present invention, the second initiator preferably includes initiator A203.

[0035] In the present invention, the temperature of the first copolymerization reaction is 50 to 85° C., preferably 60 to 80° C.; the time is preferably 0.1 to 0.5 h, more preferably 0.15 to 0.2 h.

[0036] In the present invention, the mass ratio of the first copolymer to the second initiator is preferably 1:1.

[0037] In the present invention, the first copolymer and the second initiator are mixed preferably by dripping the second initiator into the first copolymer. In the present invention, the dripping rate is preferably 10 to 40 drops / min, more preferably 20 to 35 drops / min.

[0038] In the present invention, the temperature of the second copolymerization reaction is 60-85°C, preferably 70°C; the time is preferably 30-90 min, more preferably 60 min.

[0039] The technical solutions provided by the present invention are described in detail below in conjunction with the embodiments, but they should not be construed as limiting the protection scope of the present invention.

[0040] Example 1

[0041] 5 g of an emulsifier, 2 g of a modifier, 3 g of a cross-linking agent, 100 g of a polymer intermediate and 0.02 g of a first initiator were mixed at a rotation speed of 45 rpm for 30 min, and then a first copolymerization reaction was carried out at 60° C. for 0.3 h to obtain a first copolymer;

[0042] 110 g of the first copolymer and 0.02 g of the second initiator A203 were mixed at a rotation speed of 25 rpm for 20 min, and then a second copolymerization reaction was carried out at 70° C. for 120 min to obtain the modified acrylic resin.

[0043] The emulsifier is specifically K12 emulsifier;

[0044] The modifier is specifically methylvinylchlorosilane;

[0045] The cross-linking agent is specifically AAEM;

[0046] The polymerizable monomer is specifically methyl acrylate;

[0047] The first initiator is specifically ammonium persulfate;

[0048] The second initiator is specifically ammonium persulfate.

[0049] Comparative Example 1

[0050] The only difference from Example 1 is that the second copolymerization reaction is not carried out.

[0051] Test example:

[0052] The present invention tests the yield of the modified acrylic resin prepared in Example 1 and Comparative Example 1. The yield of Example 1 is 90%, and the yield of Comparative Example 1 is 80%.

[0053] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A method for preparing a modified acrylic resin, characterized in that: The following steps are involved: An emulsifier, a modifier, a cross-linking agent, a polymerization monomer and a first initiator are mixed to carry out a first copolymerization reaction to obtain a first copolymer; The first copolymer and the second initiator are mixed to carry out a second copolymerization reaction to obtain the modified acrylic resin; the crosslinking agent includes acetoacetoxyethyl methacrylate; The polymerizable monomer includes at least one of a hard monomer, a soft monomer, a functional monomer or a water-soluble monomer; the hard monomer includes one or more of methyl acrylate, methyl methacrylate, ethyl acrylate and styrene; The temperature of the first copolymerization reaction is 50-85°C; the temperature of the second copolymerization reaction is 60-85°C.

2. The preparation method according to claim 1, characterized in that: The emulsifier includes one or more of K12 emulsifier, NP-10 emulsifier, EPA 1963 emulsifier, EPA073 emulsifier, PF20S emulsifier, DSA 502 emulsifier, Hostaphat 1308 emulsifier, CPA 100 emulsifier, CPA100XS emulsifier, LCN118 emulsifier, LCN287 emulsifier, LCN407 emulsifier, UD030 emulsifier, UD 050 emulsifier, UD110 emulsifier, X088 emulsifier, X307 emulsifier, X407 emulsifier, X1005 emulsifier, PF10 emulsifier, PF20 emulsifier, PF40 emulsifier, PF80 emulsifier, 2A1 emulsifier, A102 emulsifier and Cytec OT75 emulsifier.

3. The preparation method according to claim 1, characterized in that: The modifier includes one or more of vegetable oil acid, epoxy soybean oil, methylchlorosilane, phenylchlorosilane, methylvinylchlorosilane, ethyltrichlorosilane, propyltrichlorosilane, vinyltrichlorosilane, gamma-chloropropyltrichlorosilane and fluorosilicon monomer.

4. The preparation method according to claim 1, characterized in that: The water-soluble monomers include methylene succinic acid and / or acrylic acid.

5. The preparation method according to claim 1, characterized in that: The soft monomer includes one or more of ethyl methacrylate, butyl acrylate, butyl methacrylate, isooctyl acrylate, isooctyl methacrylate and tert-butyl methacrylate.

6. The preparation method according to claim 1, characterized in that: The functional monomers include one or more of acrylamide, methacrylamide, N-hydroxymethyl acrylamide and N-hydroxyethyl acrylamide, glycidyl acrylate, glycidyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, lauryl acrylate, lauryl methacrylate, octadecyl acrylate, octadecyl methacrylate, cyclohexyl methacrylate, trifluoroethyl methacrylate, vinyl acetate, versatate vinyl carbonate, dicyclopentadienyl acrylate, dicyclopentadienyl methacrylate, isobornyl acrylate, isobornyl methacrylate, diallyl phthalate, allyl methacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, vinyl trimethoxysilane, vinyl triethoxysilane and γ-methacryloxypropyl trimethoxysilane.

7. The preparation method according to any one of claims 1 to 6, characterized in that: The first copolymerization reaction time is 0.1 to 0.3 h.

8. The preparation method according to any one of claims 1 to 6, characterized in that: The second copolymerization reaction time is 30 to 90 minutes.