Modified acrylic polyurethane resin, preparation method thereof and sizing material

Abstract

The invention relates to the field of chemical engineering, in particular to modified acrylic polyurethane resin, a preparation method thereof and a sizing material. The invention provides a preparation method of modified acrylic polyurethane, which comprises the following steps: a) mixing an epoxy diluent, acrylic polyurethane, glycidyl acrylate, an acrylate monomer, a link transfer agent and an initiator for reaction to obtain epoxy modified acrylic polyurethane resin; and b) mixing the epoxy modified acrylic polyurethane resin with a ring-opening catalyst, a polymerization inhibitor and a (methyl) acrylic monomer for reaction to obtain the modified acrylic polyurethane resin. The modified acrylic polyurethane resin provided by the invention can effectively reduce the UV curing shrinkage rate, and ensures that the material has high strength and high toughness.

Description

Technical Field

[0001] The invention relates to the field of chemical industry, and in particular to a modified acrylic polyurethane resin and a preparation method thereof, as well as a rubber material. Background Art

[0002] In the prior art, in order to reduce the shrinkage rate of the UV curing system, some improvement methods are often introduced, but there are usually different disadvantages. They are roughly as follows: 1. Add spirocyclic substances and open the ring to offset the shrinkage rate; the disadvantages of this method: the synthesis of spirocyclic compounds is difficult, the cost is high, and the marketability is very low. 2. Use epoxy structure UV curing, and use the principle of low epoxy ring opening shrinkage rate to achieve the purpose of reducing the curing shrinkage rate; the disadvantages of this method: UV-cured epoxy resin has strong rigidity, poor toughness, and general weather resistance (especially in terms of transparent glue requirements). 3. Reduce the double bond content, such as adding a large amount of plasticizers, solid resins, fillers and other inactive substances; the disadvantages of this method: inactive substances do not participate in the UV curing reaction, the curing product has low reaction activity and low cross-linking degree, resulting in low strength after curing, which is difficult to apply to high-strength requirements. It can be seen that when the prior art attempts to reduce curing shrinkage through some improvement methods, it will bring about the degradation of other aspects of performance, such as reduced toughness and strength. Summary of the invention

[0003] In view of this, the present invention provides a modified acrylic polyurethane resin and a preparation method thereof, as well as a sizing material. The modified acrylic polyurethane resin provided by the present invention can effectively reduce the UV curing shrinkage rate while ensuring that the material has high strength and high toughness.

[0004] The present invention provides a method for preparing a modified acrylic polyurethane, comprising the following steps:

[0005] a) mixing and reacting an epoxy diluent, acrylic polyurethane, glycidyl acrylate, an acrylate monomer, a link transfer agent and an initiator to obtain an epoxy-modified acrylic polyurethane resin;

[0006] b) mixing the epoxy-modified acrylic polyurethane resin with a ring-opening catalyst, a polymerization inhibitor and a (meth)acrylic acid monomer to obtain a modified acrylic polyurethane resin.

[0007] Preferably, in step a), the acrylic polyurethane is CR92958.

[0008] Preferably, in step a):

[0009] The epoxy diluent is at least one of alkylene glycidyl ether, epoxy soybean oil, ethylene glycol diglycidyl ether, butyl glycidyl ether and neopentyl glycol diglycidyl ether;

[0010] The acrylic acid ester monomer is at least one of isooctyl acrylate, lauric (meth)acrylate, butyl (meth)acrylate, isobornyl (meth)acrylate and dimethylacrylamide;

[0011] The chain transfer agent is CR92509;

[0012] The reaction temperature is 80-130° C. and the reaction time is 2-5 hours.

[0013] Preferably, in step a), the amount of each material used is as follows, in parts by mass:

[0014]

[0015] Preferably, in step b);

[0016] The ring-opening catalyst is at least one of N,N-dimethylbenzylamine, triphenylphosphine, triethylamine and tetraethylammonium bromide;

[0017] The polymerization inhibitor is at least one of the polymerization inhibitors MEHQ, TBC and HQ.

[0018] Preferably, in step b), the reaction temperature is 105-115°C.

[0019] Preferably, in step b), the amount of each material used is as follows, in parts by mass:

[0020]

[0021] Preferably, step a) specifically comprises:

[0022] a1) mixing glycidyl acrylate, an acrylate monomer, a chain transfer agent and an initiator to obtain a mixture;

[0023] a2) under a protective atmosphere, adding acrylic polyurethane and epoxy diluent into a reaction kettle, stirring evenly, heating to a target temperature, and adding dropwise the mixture obtained in step a1) to react, thereby obtaining an epoxy-modified acrylic polyurethane resin;

[0024] Step b) specifically comprises: cooling the epoxy-modified acrylic polyurethane resin to 80-105° C., then adding a polymerization inhibitor and a ring-opening catalyst, stirring evenly, adding (meth)acrylic acid and continuing to stir evenly; then, heating to 105-115° C. for heat preservation reaction until the acid value is ≤5 mgKOH / g, and then terminating the reaction to obtain a modified acrylic polyurethane resin.

[0025] The present invention also provides a modified acrylic polyurethane resin prepared by the preparation method described in the above technical scheme.

[0026] The present invention also provides a rubber material, which comprises, by weight:

[0027]

[0028] Wherein, the resin is the modified acrylic polyurethane resin described in the above technical solution.

[0029] The preparation method of the modified acrylic polyurethane provided by the present invention comprises the following steps: firstly, epoxy diluent, acrylic polyurethane, glycidyl (meth)acrylate, acrylate monomer, chain transfer agent and initiator are mixed and reacted to obtain epoxy-modified acrylic polyurethane resin; then, the epoxy-modified acrylic polyurethane resin is mixed and reacted with a polymerization inhibitor, a ring-opening catalyst and (meth)acrylic acid to obtain a modified acrylic polyurethane resin. The present invention synthesizes the modified acrylic polyurethane resin by a solvent-free method, prepolymerizes the acrylic polyurethane with the double bonds in the functional acrylate monomer, controls the molecular weight of the obtained modified acrylic polyurethane resin by a chain transfer agent, and appropriately connects the acrylate group by epoxy ring opening, introduces photocuring activity and effectively regulates the volume shrinkage rate of the UV curing process. The modified acrylic polyurethane provided by the present invention can be used for UV curing resin, improves its workability, reduces the curing volume shrinkage rate, and improves the material toughness and tensile shear strength.

[0030] The test results show that the modified acrylic polyurethane prepared by the present invention has moderate viscosity, a curing energy below 1100mJ / cm2, a hardness of 40-60D and a flexibility diameter below 2mm, a tensile shear strength of more than 5MPa, and a UV curing volume shrinkage rate of no more than 3%, showing excellent flexibility, strength and good workability. DETAILED DESCRIPTION

[0031] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art to which this application belongs. The terms used herein in the specification of this application are only for the purpose of describing specific embodiments and are not intended to limit this application.

[0032] In this article, the technical features described in an open manner include closed technical solutions composed of the listed features, and also include open technical solutions containing the listed features.

[0033] As used herein, the term "and / or" includes any and all combinations of one or more of the associated listed items.

[0034] Herein, when it comes to numerical ranges, unless otherwise specified, the numerical ranges are deemed to be continuous and include the minimum and maximum values ​​of the range, as well as every value between such minimum and maximum values. Further, when a range refers to an integer, every integer between the minimum and maximum values ​​of the range is included. In addition, when multiple ranges are provided to describe features or characteristics, the ranges can be merged. In other words, unless otherwise specified, all ranges disclosed herein should be understood to include any and all subranges included therein.

[0035] In this article, when referring to the unit of a data range, if there is a unit only after the right endpoint, it means that the units of the left and right endpoints are the same. For example, 80-130℃ means that the units of the left endpoint "80" and the right endpoint "130" are both ℃.

[0036] The present invention provides a method for preparing a modified acrylic polyurethane, comprising the following steps:

[0037] a) mixing and reacting an epoxy diluent, acrylic polyurethane, glycidyl acrylate, an acrylate monomer, a link transfer agent and an initiator to obtain an epoxy-modified acrylic polyurethane resin;

[0038] b) mixing the epoxy-modified acrylic polyurethane resin with a ring-opening catalyst, a polymerization inhibitor and a (meth)acrylic acid monomer to obtain a modified acrylic polyurethane resin.

[0039] The modified acrylic polyurethane provided by the invention is an ultraviolet (UV) curing resin, which can significantly reduce the volume shrinkage of epoxy resin curing, while maintaining the original curing efficiency and improving its toughness and strength.

[0040] [About step a]:

[0041] a) mixing and reacting an epoxy diluent, acrylic polyurethane, glycidyl acrylate, an acrylate monomer, a link transfer agent and an initiator to obtain an epoxy-modified acrylic polyurethane resin.

[0042] In the present invention, the epoxy diluent is preferably at least one of alkylene glycidyl ether, epoxy soybean oil, ethylene glycol diglycidyl ether, butyl glycidyl ether and neopentyl glycol diglycidyl ether, and more preferably alkylene glycidyl ether. The present invention has no particular limitation on the source of the epoxy diluent, and it can be a commercial product.

[0043] In the present invention, the acrylic polyurethane is preferably CR92958, which is a difunctional acrylic polyurethane resin provided by Guangdong Haohui New Materials Co., Ltd.

[0044] In the present invention, the acrylic acid ester monomer is preferably at least one of isooctyl acrylate, lauric (meth)acrylate, butyl (meth)acrylate, isobornyl (meth)acrylate and dimethylacrylamide. Wherein, the lauric (meth)acrylate is lauric acrylate and / or lauric methacrylate. The butyl (meth)acrylate is butyl acrylate and / or butyl methacrylate. The isobornyl (meth)acrylate is isobornyl acrylate and / or isobornyl methacrylate. In the present invention, the acrylic acid ester monomer is more preferably isooctyl acrylate, isobornyl acrylate and dimethylacrylamide. In the present invention, when the acrylic acid ester monomers are isooctyl acrylate, isobornyl acrylate and dimethyl acrylamide, the mass ratio of isooctyl acrylate: isobornyl acrylate: dimethyl acrylamide is preferably 1: (0.2-0.6): (0.1-0.3), specifically 1: 0.2: 0.1, 1: 0.2: 0.2, 1: 0.2: 0.3, 1: 0.3: 0.1, 1: 0.3: 0.2, 1: 0.3: 0.25, 1: 0.3: 0.3, 1: 0.4: 0.1, 1: 0.4: 0.2, 1: 0.4: 0.3, 1: 0.5: 0.1, 1: 0.5: 0.2, 1: 0.5: 0.3, 1: 0.6: 0.1, 1: 0.6: 0.15, 1: 0.6: 0.2, 1: 0.6: 0.3. The present invention has no particular limitation on the source of the acrylic ester monomer, and any commercial product may be used.

[0045] In the present invention, the chain transfer agent is preferably CR92509, which is a multifunctional mercapto compound provided by Guangdong Haohui New Materials Co., Ltd.

[0046] In the present invention, the initiator is preferably at least one of initiator AIBN and initiator BPO. The present invention has no particular limitation on the source of the initiator, and it can be a commercial product.

[0047] In the present invention, in step a), the amount of each material used is as follows, in parts by mass:

[0048]

[0049] Wherein: the amount of the acrylic polyurethane can be 40 parts, 45 parts, 50 parts, 55 parts, 60 parts, 65 parts, 70 parts, 75 parts, 80 parts, 85 parts, 90 parts, 95 parts, 100 parts, 105 parts, 110 parts, 115 parts, 120 parts, 125 parts, 130 parts, 135 parts, 140 parts, 145 parts, 150 parts. The amount of the glycidyl acrylate can be 10 parts, 15 parts, 20 parts, 25 parts, 30 parts. The amount of the acrylic ester monomer can be 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts, 50 parts, 55 parts, 60 parts, 65 parts, 70 parts, 75 parts, 80 parts. The amount of the chain transfer agent can be 0.1 part, 0.2 part, 0.3 part, 0.4 part, 0.5 part, 0.6 part, 0.7 part, 0.8 part, 0.9 part, 1.0 part. The amount of the initiator can be 1 part, 2 parts, 3 parts, 4 parts, 5 parts.

[0050] In the present invention, the reaction is preferably carried out under a protective atmosphere. The present invention has no particular limitation on the type of gas providing the protective atmosphere, and any conventional protective gas well known to those skilled in the art may be used, such as nitrogen or argon.

[0051] In the present invention, the reaction temperature is preferably 80-130°C, specifically 80°C, 85°C, 90°C, 95°C, 100°C, 105°C, 110°C, 115°C, 120°C, 125°C, 130°C. In the present invention, the reaction time is preferably 2-5h, specifically 2h, 3h, 4h, 5h. After the reaction, an epoxy-modified acrylic polyurethane resin is obtained.

[0052] In the present invention, step a) preferably specifically comprises:

[0053] a1) mixing glycidyl acrylate, an acrylate monomer, a chain transfer agent and an initiator to obtain a mixture;

[0054] a2) Under a protective atmosphere, acrylic polyurethane and epoxy diluent are put into a reaction kettle, stirred evenly, heated to the target temperature, and the mixture obtained in step a1) is added dropwise to react to obtain epoxy-modified acrylic polyurethane resin.

[0055] Regarding step a1): the mixing method is not particularly limited, and the materials can be mixed uniformly according to conventional mixing operations in the art, such as stirring and mixing. After uniform mixing, a mixture is obtained.

[0056] Regarding step a2): the specific operation can be as follows: put the acrylic polyurethane and epoxy diluent into a reaction kettle, stir and disperse them evenly, then heat to the target reaction temperature under a protective atmosphere, and then drop the mixture obtained in step a1) to react to obtain epoxy-modified acrylic polyurethane resin. The type of gas providing the protective atmosphere is the same as described above. The temperature and reaction time of the heating reaction are as described above, and will not be repeated here. After the reaction, epoxy-modified acrylic polyurethane resin is obtained.

[0057] [About step b]:

[0058] b) mixing the epoxy-modified acrylic polyurethane resin with a ring-opening catalyst, a polymerization inhibitor and a (meth)acrylic acid monomer to obtain a modified acrylic polyurethane resin.

[0059] In the present invention, the ring-opening catalyst is preferably at least one of N,N-dimethylbenzylamine, triphenylphosphine, triethylamine and tetraethylammonium bromide. The present invention has no particular limitation on the source of the ring-opening catalyst, and it can be a commercial product.

[0060] In the present invention, the polymerization inhibitor is preferably at least one of the polymerization inhibitors MEHQ, TBC and HQ. The present invention has no particular limitation on the source of the polymerization inhibitor, and it can be a commercial product.

[0061] In the present invention, the (meth)acrylic acid monomer is an acrylic acid monomer and / or a (meth)acrylic acid monomer. The present invention has no particular limitation on the source of the (meth)acrylic acid monomer, and it can be a commercial product.

[0062] In the present invention, in step b), the amount of each material used is preferably as follows, in parts by mass:

[0063]

[0064] Wherein: the dosage of the polymerization inhibitor can be 0.1 parts, 0.2 parts, 0.3 parts, 0.4 parts, 0.5 parts. The dosage of the ring-opening catalyst can be 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts, 0.9 parts, 1.0 parts. The dosage of the (meth)acrylic acid can be 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, 20 parts.

[0065] In the present invention, the reaction temperature is preferably 105-115° C., specifically 105° C., 106° C., 107° C., 108° C., 109° C., 110° C., 111° C., 112° C., 113° C., 114° C., 115° C. The degree of the reaction is preferably until the acid value is ≤5 mgKOH / g. After the reaction, a modified acrylic polyurethane resin is obtained.

[0066] In the present invention, the above step b) preferably specifically comprises: cooling the epoxy-modified acrylic polyurethane resin to 80-105° C., then adding a polymerization inhibitor and a ring-opening catalyst, stirring evenly, adding (meth)acrylic acid and continuing to stir evenly; then, heating to 105-115° C. for heat preservation reaction until the acid value is ≤5 mgKOH / g, terminating the reaction, and obtaining a modified acrylic polyurethane resin.

[0067] The present invention also provides a modified acrylic polyurethane resin prepared by the preparation method described in the above technical scheme.

[0068] The present invention also provides a rubber material, which comprises, by weight:

[0069]

[0070]

[0071] Wherein, the resin is the modified acrylic polyurethane resin described in the above technical solution.

[0072] The amount of the resin can be 70 parts, 75 parts, 80 parts, 85 parts, and 90 parts. The amount of the isobornyl acrylate can be 5 parts, 8 parts, 11 parts, 14 parts, 17 parts, and 20 parts. The amount of the morpholine acrylate can be 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, and 10 parts. The photoinitiator is preferably a photoinitiator TPO. The amount of the photoinitiator can be 0.1 parts, 0.5 parts, 1.0 parts, 1.5 parts, 2.0 parts, 2.5 parts, 3.0 parts, 3.5 parts, 4.0 parts, 4.5 parts, and 5.0 parts. The adhesion promoter is preferably KH560. The specific usage of the adhesion promoter can be 0.01 parts, 0.05 parts, 0.10 parts, 0.50 parts, 1.0 parts, 1.5 parts, 2.0 parts, 2.5 parts, 3.0 parts.

[0073] The preparation method of the modified acrylic polyurethane provided by the present invention comprises the following steps: firstly, epoxy diluent, acrylic polyurethane, glycidyl (meth)acrylate, acrylate monomer, chain transfer agent and initiator are mixed and reacted to obtain epoxy-modified acrylic polyurethane resin; then, the epoxy-modified acrylic polyurethane resin is mixed and reacted with a polymerization inhibitor, a ring-opening catalyst and (meth)acrylic acid to obtain a modified acrylic polyurethane resin. The present invention synthesizes the modified acrylic polyurethane resin by a solvent-free method, prepolymerizes the acrylic polyurethane with the double bonds in the functional acrylate monomer, controls the molecular weight of the obtained modified acrylic polyurethane resin by a chain transfer agent, and appropriately connects the acrylate group by epoxy ring opening, introduces photocuring activity and effectively regulates the volume shrinkage rate of the UV curing process. The modified acrylic polyurethane provided by the present invention can be used for UV curing resin, improves its workability, reduces the curing volume shrinkage rate, and improves the material toughness and tensile shear strength.

[0074] The performance of UV cured products is mainly affected by the performance of resins and monomers, and the main factor for the shrinkage rate of UV curing is that the bond length is greatly reduced after the C=C double bond is broken to form a CC single bond during the UV curing process of the resin or monomer, resulting in a reduction in the volume of the cured product, that is, shrinkage. Among them, the UV monomer has the greatest impact, because the monomer has a low molecular weight and a high double bond density, and direct curing will inevitably cause a large shrinkage rate. The present invention only uses a small amount of or no inactive substances to maintain the excellent performance of the resin and the formulation, and prepolymerizes the reactive components (double bonds in the resin or monomer) in the resin and the formulation through a free radical thermal polymerization reaction, controls the molecular weight of the polymerization reaction product, achieves a suitable construction viscosity, greatly reduces the double bond content, and can maintain the excellent performance of the solution (such as improving toughness, maintaining high strength, etc.); that is, the present invention reacts the double bond components (mainly monomers) in the solution in advance through a prepolymerization reaction, directly reduces the double bond density before UV curing, thereby achieving the purpose of low curing shrinkage after UV curing, and can also solve the problem of extremely rapid increase in viscosity of solid resins (fillers) and difficult construction.

[0075] The test results show that the modified acrylic polyurethane prepared by the present invention has moderate viscosity, a curing energy below 1100mJ / cm2, a hardness of 40-60D and a flexibility diameter below 2mm, a tensile shear strength of more than 5MPa, and a UV curing volume shrinkage rate of no more than 3%, showing excellent flexibility, strength and good workability.

[0076] In order to further understand the present invention, preferred embodiments of the present invention are described below in conjunction with examples. However, it should be understood that these descriptions are only for further illustrating the features and advantages of the present invention, rather than limiting the claims of the present invention.

[0077] Example 1

[0078] a1) putting glycidyl acrylate, acrylic acid ester monomers (isooctyl acrylate, isobornyl acrylate, dimethyl acrylamide), chain transfer agent CR92509 and initiator BPO into a dropping tank and stirring evenly to obtain a mixture;

[0079] a2) Under nitrogen protection, acrylic polyurethane CR92958 and epoxy diluent (alkylene glycidyl ether) were added into a reaction kettle, stirred evenly, and then heated to 105° C., and the mixture obtained in step a1) was added dropwise, and reacted for 3.5 hours to obtain epoxy-modified acrylic polyurethane resin;

[0080] The amount of each material is as follows:

[0081]

[0082] Among the acrylic ester monomers, the mass ratio of isooctyl acrylate:isobornyl acrylate:dimethylacrylamide is 1:0.4:0.2.

[0083] b) cooling the obtained epoxy-modified acrylic polyurethane resin to 90° C., adding a polymerization inhibitor HQ and a ring-opening catalyst N,N-dimethylbenzylamine, stirring evenly, adding acrylic acid and continuing to stir evenly; then, heating to 110° C., keeping the temperature to react until the acid value is ≤5 mgKOH / g, and obtaining a modified acrylic polyurethane resin;

[0084] The amount of each material is as follows:

[0085]

[0086]

[0087] Example 2

[0088] a1) putting glycidyl acrylate, acrylic acid ester monomers (isooctyl acrylate, isobornyl acrylate, dimethyl acrylamide), chain transfer agent CR92509 and initiator BPO into a dropping tank and stirring evenly to obtain a mixture;

[0089] a2) Under nitrogen protection, acrylic polyurethane CR92958 and epoxy diluent (alkylene glycidyl ether) were added into a reaction kettle, stirred evenly, and then heated to 105° C., and the mixture obtained in step a1) was added dropwise, and reacted for 3.5 hours to obtain epoxy-modified acrylic polyurethane resin;

[0090] The amount of each material is as follows:

[0091]

[0092] Among the acrylic ester monomers, the mass ratio of isooctyl acrylate:isobornyl acrylate:dimethylacrylamide is 1:0.5:0.1.

[0093] b) cooling the obtained epoxy-modified acrylic polyurethane resin to 90° C., adding a polymerization inhibitor HQ and a ring-opening catalyst N,N-dimethylbenzylamine, stirring evenly, adding acrylic acid and continuing to stir evenly; then, heating to 110° C., keeping the temperature to react until the acid value is ≤5 mgKOH / g, and obtaining a modified acrylic polyurethane resin.

[0094] The amount of each material is as follows:

[0095]

[0096] Example 3

[0097] a1) putting glycidyl acrylate, acrylic acid ester monomers (isooctyl acrylate, isobornyl acrylate, dimethyl acrylamide), chain transfer agent CR92509 and initiator BPO into a dropping tank and stirring evenly to obtain a mixture;

[0098] a2) Under nitrogen protection, acrylic polyurethane CR92958 and epoxy diluent (alkylene glycidyl ether) were added into a reaction kettle, stirred evenly, and then heated to 105° C., and the mixture obtained in step a1) was added dropwise, and reacted for 3.5 hours to obtain epoxy-modified acrylic polyurethane resin;

[0099] The amount of each material is as follows:

[0100]

[0101] Among the acrylic ester monomers, the mass ratio of isooctyl acrylate:isobornyl acrylate:dimethylacrylamide is 1:0.2:0.3.

[0102] b) cooling the obtained epoxy-modified acrylic polyurethane resin to 90° C., adding a polymerization inhibitor HQ and a ring-opening catalyst N,N-dimethylbenzylamine, stirring evenly, adding acrylic acid and continuing to stir evenly; then, heating to 110° C., keeping the temperature to react until the acid value is ≤5 mgKOH / g, and obtaining a modified acrylic polyurethane resin.

[0103] The amount of each material is as follows:

[0104]

[0105] Example 4

[0106] a1) putting glycidyl acrylate, acrylic acid ester monomers (isooctyl acrylate, isobornyl acrylate, dimethyl acrylamide), chain transfer agent CR92509 and initiator BPO into a dropping tank and stirring evenly to obtain a mixture;

[0107] a2) Under nitrogen protection, acrylic polyurethane CR92958 and epoxy diluent (alkylene glycidyl ether) were added into a reaction kettle, stirred evenly, and then heated to 105° C., and the mixture obtained in step a1) was added dropwise, and reacted for 3.5 hours to obtain epoxy-modified acrylic polyurethane resin;

[0108] The amount of each material is as follows:

[0109]

[0110] Among the acrylic ester monomers, the mass ratio of isooctyl acrylate:isobornyl acrylate:dimethylacrylamide is 1:0.6:0.15.

[0111] b) cooling the obtained epoxy-modified acrylic polyurethane resin to 90° C., adding a polymerization inhibitor HQ and a ring-opening catalyst N,N-dimethylbenzylamine, stirring evenly, adding acrylic acid and continuing to stir evenly; then, heating to 110° C., keeping the temperature to react until the acid value is ≤5 mgKOH / g, and obtaining a modified acrylic polyurethane resin.

[0112] The amount of each material is as follows:

[0113]

[0114] Example 5

[0115] a1) putting glycidyl acrylate, acrylic acid ester monomers (isooctyl acrylate, isobornyl acrylate, dimethyl acrylamide), chain transfer agent CR92509 and initiator BPO into a dropping tank and stirring evenly to obtain a mixture;

[0116] a2) Under nitrogen protection, acrylic polyurethane CR92958 and epoxy diluent (alkylene glycidyl ether) were added into a reaction kettle, stirred evenly, and then heated to 105° C., and the mixture obtained in step a1) was added dropwise, and reacted for 3.5 hours to obtain epoxy-modified acrylic polyurethane resin;

[0117] The amount of each material is as follows:

[0118]

[0119]

[0120] Among the acrylic ester monomers, the mass ratio of isooctyl acrylate:isobornyl acrylate:dimethylacrylamide is 1:0.3:0.25.

[0121] b) cooling the obtained epoxy-modified acrylic polyurethane resin to 90° C., adding a polymerization inhibitor HQ and a ring-opening catalyst N,N-dimethylbenzylamine, stirring evenly, adding acrylic acid and continuing to stir evenly; then, heating to 110° C., keeping the temperature to react until the acid value is ≤5 mgKOH / g, and obtaining a modified acrylic polyurethane resin.

[0122] The amount of each material is as follows:

[0123]

[0124] Comparative Example 1

[0125] The process was carried out in accordance with Example 1, except that the epoxy diluent in step a2) was replaced by butyl acetate.

[0126] Comparative Example 2

[0127] The process was carried out in accordance with Example 2, except that glycidyl acrylate was not added in step a1), and acrylic polyurethane CR92958 was not added in step a2).

[0128] Product Testing :

[0129] 1. Preparation of rubber

[0130] (1.1) The composition of the rubber compound is as follows:

[0131]

[0132] The resins are respectively the resin products obtained in Examples 1-5 and Comparative Examples 1-2.

[0133] (1.2) Preparation of rubber compound:

[0134] Put the above materials into a mixer and stir them evenly to obtain a rubber compound.

[0135] 2. Performance Testing

[0136] ①Viscosity: Refer to GB / T 2794-2022 to test the viscosity of the sample.

[0137] ②Curing energy: Apply the rubber on the substrate and cure it with an electrodeless mercury lamp to test the curing energy required for the rubber to dry on the surface. The higher the required curing energy, the lower the curing speed.

[0138] ③Hardness: Apply the adhesive on the substrate and cure it with an electrodeless mercury lamp. The thickness of the adhesive layer is 2mm. After curing for 2 minutes, test the hardness of the paint film.

[0139] ④Flexibility: Refer to GB / T 1731-1993 to test the flexibility of the paint film. The minimum rod shaft diameter (mm) that does not cause damage to the paint film is used to represent the flexibility of the paint film. The smaller the diameter, the better the flexibility of the paint film.

[0140] ⑤Tensile shear strength: The tensile shear strength of the test sample between two PC sheets (GB / T 7124-2008 sample preparation) is tested with reference to the national standard GB / T 7124-2008.

[0141] ⑥ Volume shrinkage: Refer to ISO3521:1997 to test the density of the sample before and after curing, and then calculate the shrinkage based on the density. Shrinkage = (p after - p before) / p after × 100%, where p after and p before are the density after and before curing, respectively.

[0142] The test results are shown in Table 1:

[0143] Table 1: Sample test results

[0144]

[0145] It can be seen from the test results in Table 1 that the resin products obtained in Examples 1-5 of the present invention have moderate viscosity and a curing energy of 1100 mJ / cm 2 The hardness is 40-60D and the flexibility diameter is below 2mm, the tensile shear strength is above 5MPa, and the UV curing volume shrinkage is not more than 3%, showing excellent construction performance, fast curing speed, excellent flexibility and tensile shear strength. Compared with the embodiment, the resin product of comparative example 1-2 has low tensile shear strength, and the curing shrinkage is above 4%, and the comprehensive performance of various aspects is poor.

[0146] Specific examples are used herein to illustrate the principles and implementation methods of the present invention. The description of the above embodiments is only used to help understand the method of the present invention and its core ideas, including the best mode, and also enable any technician in the field to practice the present invention, including making and using any device or system, and implementing any combined method. It should be pointed out that for ordinary technicians in this technical field, without departing from the principle of the present invention, the present invention can also be improved and modified, and these improvements and modifications also fall within the scope of protection of the claims of the present invention. The scope of patent protection of the present invention is defined by the claims and may include other embodiments that can be thought of by those skilled in the art. If these other embodiments have structural elements similar to the literal expression of the claims, or if they include equivalent structural elements that are not substantially different from the literal expression of the claims, then these other embodiments should also be included in the scope of the claims.

Claims

1. A method for preparing modified acrylic polyurethane, characterized in that: The following steps are involved: a) mixing and reacting an epoxy diluent, acrylic polyurethane, glycidyl acrylate, an acrylate monomer, a link transfer agent and an initiator to obtain an epoxy-modified acrylic polyurethane resin; b) mixing the epoxy-modified acrylic polyurethane resin with a ring-opening catalyst, a polymerization inhibitor and a (meth)acrylic acid monomer to obtain a modified acrylic polyurethane resin.

2. The preparation method according to claim 1, characterized in that: In step a), the acrylic polyurethane is CR92958.

3. The preparation method according to claim 1, characterized in that: In step a): The epoxy diluent is at least one of alkylene glycidyl ether, epoxy soybean oil, ethylene glycol diglycidyl ether, butyl glycidyl ether and neopentyl glycol diglycidyl ether; The acrylic acid ester monomer is at least one of isooctyl acrylate, lauric (meth)acrylate, butyl (meth)acrylate, isobornyl (meth)acrylate and dimethylacrylamide; The chain transfer agent is CR92509; The reaction temperature is 80-130° C. and the reaction time is 2-5 hours.

4. The preparation method according to any one of claims 1 to 3, characterized in that In step a), the amount of each material used is as follows by weight:

5. The preparation method according to claim 1, characterized in that: In step b); The ring-opening catalyst is at least one of N,N-dimethylbenzylamine, triphenylphosphine, triethylamine and tetraethylammonium bromide; The polymerization inhibitor is at least one of polymerization inhibitor MEHQ, TBC and polymerization inhibitor HQ.

6. The preparation method according to claim 1, characterized in that: In step b), the reaction temperature is 105-115°C.

7. The preparation method according to claim 1, characterized in that: In step b), the amount of each material used is as follows by weight:

8. The preparation method according to claim 1, characterized in that: Step a) specifically includes: a1) mixing glycidyl acrylate, an acrylate monomer, a chain transfer agent and an initiator to obtain a mixture; a2) under a protective atmosphere, adding acrylic polyurethane and epoxy diluent into a reaction kettle, stirring evenly, heating to a target temperature, and adding dropwise the mixture obtained in step a1) to react, thereby obtaining an epoxy-modified acrylic polyurethane resin; Step b) specifically comprises: cooling the epoxy-modified acrylic polyurethane resin to 80-105° C., then adding a polymerization inhibitor and a ring-opening catalyst, stirring evenly, adding (meth)acrylic acid and continuing to stir evenly; then, heating to 105-115° C. for heat preservation reaction until the acid value is ≤5 mgKOH / g, and then terminating the reaction to obtain a modified acrylic polyurethane resin.

9. A modified acrylic polyurethane resin obtained by the preparation method according to any one of claims 1 to 8.

10. A rubber material, characterized in that: In parts by mass, including: Wherein, the resin is the modified acrylic polyurethane resin as described in claim 9.

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