Modified methyl methacrylate resin as well as preparation method and application thereof

Abstract

The invention relates to modified methyl methacrylate resin as well as a preparation method and application thereof, and relates to the technical field of resin materials. The modified methyl methacrylate resin comprises the following components: 50-60 parts of a methyl methacrylate monomer, 25-35 parts of an n-butyl acrylate monomer, 1-2 parts of a methacrylic acid monomer, 2-3 parts of a trimethylolpropane triacrylate monomer, 3-5 parts of chlorinated palm oil methyl ester, 0.3-0.8 part of polyvinyl butyral, 3.4-5.7 parts of chlorinated polyether resin, 0.1-0.5 part of 2, 4, 6-trimethyl-1, 3-pentanediol monoisobutyrate, 0.1-0.5 part of a coupling agent, 0.1-0.5 part of a catalyst and 0.1-0.5 part of an antioxidant. The invention relates to a flame-retardant coating which is prepared from the following components in parts by weight: 0.2 to 0.8 part of 2, 2, 6-trimethylbenzoyldiphenoxyphosphorus, 0.5 to 1.5 parts of paraffin, 0.1 to 0.5 part of polymerization inhibitor, 0.02 to 0.05 part of initiator and 0.5 to 1 part of accelerant According to the modified methyl methacrylate resin provided by the invention, various modified materials are introduced, and the components are mutually cooperated, so that the comprehensive performance of the modified methyl methacrylate resin is remarkably improved, and the defects in the prior art are overcome.

Description

Technical Field

[0001] The invention relates to the technical field of resin materials, and in particular to a modified methyl methacrylate resin and a preparation method and application thereof. Background Art

[0002] In the field of modern coatings and materials science, the pursuit of efficient, environmentally friendly and high-performance resin materials has always been a hot topic of research. Methyl methacrylate (MMA) resin, as a type of polymer material made by copolymerization of MMA monomer, n-butyl acrylate (BA) monomer and a small amount of methacrylic acid (MAA), has shown wide application potential in many industries due to its unique fast curing characteristics and excellent physical and chemical properties, especially in the transportation industry, where its ability to quickly construct and quickly open to traffic is particularly outstanding.

[0003] The preparation process of traditional methyl methacrylate resin relies on the tertiary amine-benzoyl peroxide redox system to activate free radicals, and undergoes a series of reactions from induction period, chain activation, chain growth to chain termination, ensuring that the coating can be fully cured in a very short time (about 1 hour), and this process is almost unaffected by ambient temperature and humidity. This feature greatly improves construction efficiency and reduces construction delays and cost increases caused by environmental factors.

[0004] Acrylate monomers, including methyl methacrylate, n-butyl acrylate and methacrylic acid, constitute the main components of the resin, giving the resin a series of excellent properties. Specifically, the CC main chain structure of these monomers is stable and does not contain easily oxidized and hydrolyzed groups, which makes the resin have excellent antioxidant and dielectric resistance as well as good light resistance and outdoor aging resistance. The addition of methyl methacrylate monomer further enhances the resin's weather resistance, tensile resistance and hydrolysis resistance, which is a key factor in ensuring the long-term stable operation of the resin.

[0005] However, despite the many advantages of methyl methacrylate resin, the brittleness of its bulk polymer products has become a major bottleneck restricting its widespread application in the coating field. The high brittleness not only affects the mechanical strength and toughness of the resin coating, but also limits its application in coating materials that require excellent comprehensive performance, such as high-end architectural decoration, automotive coatings, and protective coatings in complex environments. Summary of the invention

[0006] In order to solve the above problems, the present invention provides a modified methyl methacrylate resin and a preparation method and application thereof.

[0007] In a first aspect, the present invention provides a modified methyl methacrylate resin, wherein the modified methyl methacrylate resin comprises the following components in parts by weight:

[0008] 50-60 parts of methyl methacrylate monomer, 25-35 parts of n-butyl acrylate monomer, 1-2 parts of methacrylic acid monomer, 2-3 parts of trimethylolpropane triacrylate monomer, 3-5 parts of chloropalm oil methyl ester, 0.3-0.8 parts of polyvinyl butyral, 3.4-5.7 parts of chloroether resin, 0.2-0.8 parts of 2,4,6-trimethylbenzoyldiphenoxyphosphine, 0.5-1.5 parts of paraffin, 0.1-0.5 parts of inhibitor, 0.02-0.05 parts of initiator, and 0.5-1 parts of accelerator.

[0009] Furthermore, the modified methyl methacrylate resin comprises the following components in parts by weight:

[0010] 53 parts of methyl methacrylate monomer, 31 parts of n-butyl acrylate monomer, 2 parts of methacrylic acid monomer, 2 parts of trimethylolpropane triacrylate monomer, 4 parts of chloropalm oil methyl ester, 0.5 parts of polyvinyl butyral, 5 parts of chloroether resin, 0.5 parts of 2,4,6-trimethylbenzoyldiphenoxyphosphine, 1 part of paraffin, 0.2 parts of inhibitor, 0.02 parts of initiator, and 0.8 parts of accelerator.

[0011] Furthermore, the polymerization inhibitor is obtained by compounding p-diphenol monomethyl ether and dibutyl hydroxytoluene in a weight ratio of (0.5-1):(2-5).

[0012] Furthermore, the initiator is an azo initiator, and the azo initiator includes azobisisobutyronitrile.

[0013] Furthermore, the accelerator is obtained by compounding N,N-dimethyl-p-toluidine, N,N-dihydroxyethyl-p-toluidine and dicyclopentadienyl iron in a weight ratio of (1-3):(5-8):(1-2).

[0014] Furthermore, the chloroether resin includes chloroether resin MP45, and the paraffin includes No. 52 fully refined paraffin.

[0015] In a second aspect, the present invention provides a method for preparing the modified methyl methacrylate resin according to any one of the first aspects, the preparation method comprising the following steps:

[0016] In an inert gas atmosphere, methyl methacrylate monomer, n-butyl acrylate monomer and initiator are stirred and heated to 125-135° C., then kept warm and methacrylic acid monomer is added dropwise to carry out polymerization reaction, and the viscosity of the reaction system is between 45 Pa·s and 70 Pa·s to obtain a first reaction solution;

[0017] The first reaction solution is first cooled to 75-85° C., and then paraffin, chloropalm oil methyl ester, chloroether resin, polyvinyl butyral and trimethylolpropane triacrylate monomer are added and first stirred and mixed to obtain a second reaction solution;

[0018] The second reaction solution is subjected to a second cooling down to 40-50° C., and then an accelerator, a polymerization inhibitor and 2,4,6-trimethylbenzoyldiphenoxyphosphine are added thereto for a second stirring and mixing to obtain the modified methyl methacrylate resin.

[0019] Furthermore, the dripping speed of the methacrylic acid monomer is 8-12 kg / h, the polymerization reaction time is 2.5-3.5 hours, the end point temperature of the first cooling is 80° C., and the end point temperature of the second cooling is 45° C.

[0020] Furthermore, the working condition parameters of the first stirring and mixing include: stirring time of 1 to 2 hours, stirring speed of 100 to 200 rpm; the working condition parameters of the second stirring and mixing include: stirring time of 1 to 2 hours, stirring speed of 100 to 200 rpm.

[0021] In a third aspect, the present invention provides use of the modified methyl methacrylate resin described in any one of the first aspect and the second aspect in preparing a coating.

[0022] The above technical solution provided by the embodiment of the present invention has at least the following advantages compared with the prior art:

[0023] The embodiment of the present invention provides a modified methyl methacrylate resin and a preparation method and application thereof. The modified methyl methacrylate resin provided by the present invention introduces a variety of modified materials, and adds a soft monomer n-butyl acrylate with a low glass transition temperature to modify and copolymerize methyl methacrylate during the polymerization process. The copolymerized resin has both the excellent weather resistance and tensile strength of methyl methacrylate and the excellent low-temperature flexibility of n-butyl acrylate. A small amount of methacrylic acid is introduced to improve the wettability of the resin to the substrate, thereby improving the adhesion of the coating film. The components work together to significantly improve the comprehensive performance, making up for the deficiencies of the prior art. Specifically, the functions of the main raw materials introduced in the present invention are as follows:

[0024] 1) Trimethylolpropane triacrylate monomer, referred to as TMPTA, as a tri-functional active monomer, plays a role in enhancing the activity and cross-linking of the resin in the resin of the present invention. After the induction period, it significantly accelerates the curing of the coating, shortens the curing time of the coating, and increases the cross-linking density of the coating.

[0025] 2) VOP can significantly improve the low-temperature flexibility and elongation at break of methyl methacrylate resin, and will not migrate to the outside of the coating and lose its plasticizing effect like dibutyl phthalate plasticizers.

[0026] 3) Polyvinyl butyral, referred to as PVB, although this material is insoluble in the resin of methyl methacrylate and butyl acrylate copolymer, it is embedded in the coating during the redox reaction. A small amount of addition can significantly improve the low-temperature flexibility and elongation at break of the coating, and improve the adhesion of the coating to concrete substrates, glass substrates, and marble substrates.

[0027] 4) Chloroether resin MP45. Chloroether resin can be completely dissolved in the resin copolymerized with methyl methacrylate and butyl acrylate. It can adjust the viscosity of the resin and significantly increase the wettability of the resin to pigments and fillers. Chloroether resin contains a large number of ether bonds, which can significantly enhance the adhesion of the resin to the metal substrate.

[0028] 5) Add 2,4,6-trimethylbenzoyldiphenoxyphosphine, referred to as TPO, TPO is a photoinitiator. Adding TPO to this resin can significantly improve the anti-oxidation inhibition effect under visible light environment, and improve the surface gloss, surface hardness and scratch resistance of the coating. TPO is commonly used in light-cured UV coatings, and its application in methyl methacrylate resin to improve the integrity of surface curing and solve the problem of oxygen inhibition is the first.

[0029] 6) No. 52 fully refined paraffin wax acts as a wax sealing layer. During the coating and curing process, the paraffin wax gradually migrates to the surface of the coating, forming a wax film to isolate oxygen and reduce the inhibitory effect of oxygen on free radical polymerization.

[0030] 7) A polymerization inhibitor prepared by mixing p-diphenol monomethyl ether and butylated hydroxytoluene (BHT for short). BHT is commonly used as an antioxidant in food and rubber. The use of BHT as a polymerization inhibitor for methacrylic resin is the first invention of the present invention.

[0031] 8) Azo initiators, azobisisobutyronitrile, referred to as AIBN and, begin to decompose and release free radicals at 65 degrees Celsius, activating MMA and BA for free radical polymerization, have a long half-life, and leave less resin residue after polymerization.

[0032] 9) The promoter of N, N-dimethyl-p-toluidine (DMPT for short), N, N-dihydroxyethyl-p-toluidine (DHPT for short), and dicyclopentadiene iron combination, if only a single promoter is used, can not achieve a good catalytic effect. For example, when only dimethyl-p-toluidine is used, the catalytic effect is faster, the free radicals are released quickly, the cured coating is soft and the glass transition temperature is low (about 25 degrees Celsius), which is manifested as insufficient surface hardness of the coating, which is not conducive to large-scale outdoor application. If only dihydroxyethyl-p-toluidine is used, the activity is insufficient, and the induction period is long in winter, which is not conducive to rapid construction and curing. When only ferrocene is used, the catalytic effect is unstable or difficult to react with benzoyl peroxide at a temperature below 5 degrees Celsius; but after adding ferrocene, the bridging effect of metallocene can be fully exerted to form active center points and improve the cross-linking density of the coating. Therefore, the present invention uses three promoters in combination, which can achieve a better effect in the redox reaction of tertiary amine + metallocene catalyst and benzoyl peroxide (BPO). This formula is designed to improve the product's construction practicality and physical properties, allowing it to have an appropriate induction period to leave enough time for construction, while also increasing the cross-linking density of the coating to allow the coating to cure completely. DETAILED DESCRIPTION

[0033] In order to make the purpose, technical solution and advantages of the embodiments of the present invention clearer, the technical solution in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0034] Unless otherwise specified, various raw materials, reagents, instruments and equipment used in the present invention can be purchased from the market or prepared by existing methods.

[0035] In a first aspect, the present invention provides a modified methyl methacrylate resin, wherein the modified methyl methacrylate resin comprises the following components in parts by weight:

[0036] 50-60 parts of methyl methacrylate monomer, 25-35 parts of n-butyl acrylate monomer, 1-2 parts of methacrylic acid monomer, 2-3 parts of trimethylolpropane triacrylate monomer, 3-5 parts of chloropalm oil methyl ester, 0.3-0.8 parts of polyvinyl butyral, 3.4-5.7 parts of chloroether resin, 0.2-0.8 parts of 2,4,6-trimethylbenzoyldiphenoxyphosphine, 0.5-1.5 parts of paraffin, 0.1-0.5 parts of inhibitor, 0.02-0.05 parts of initiator, and 0.5-1 parts of accelerator.

[0037] The embodiment of the present invention provides a modified methyl methacrylate resin. The modified methyl methacrylate resin provided by the present invention introduces a variety of modified materials, and adds a soft monomer n-butyl acrylate with a low glass transition temperature to modify and copolymerize methyl methacrylate during the polymerization process. The copolymerized resin has both the excellent weather resistance and tensile strength of methyl methacrylate and the excellent low-temperature flexibility of n-butyl acrylate. A small amount of methacrylic acid is introduced to improve the wettability of the resin to the substrate, thereby improving the adhesion of the coating film. The components work together to significantly improve its comprehensive performance, making up for the shortcomings of the prior art.

[0038] In some specific embodiments, the modified methyl methacrylate resin comprises the following components in parts by weight:

[0039] 53 parts of methyl methacrylate monomer, 31 parts of n-butyl acrylate monomer, 2 parts of methacrylic acid monomer, 2 parts of trimethylolpropane triacrylate monomer, 4 parts of chloropalm oil methyl ester, 0.5 parts of polyvinyl butyral, 5 parts of chloroether resin, 0.5 parts of 2,4,6-trimethylbenzoyldiphenoxyphosphine, 1 part of paraffin, 0.2 parts of inhibitor, 0.02 parts of initiator, and 0.8 parts of accelerator.

[0040] In some specific embodiments, the polymerization inhibitor is prepared by compounding p-diphenol monomethyl ether and dibutyl hydroxytoluene in a weight ratio of (0.5-1):(2-5).

[0041] In some specific embodiments, the initiator is an azo initiator, and the azo initiator includes azobisisobutyronitrile.

[0042] In some specific embodiments, the accelerator is prepared by compounding N,N-dimethyl-p-toluidine, N,N-dihydroxyethyl-p-toluidine and dicyclopentadienyl iron in a weight ratio of (1-3):(5-8):(1-2).

[0043] In some specific embodiments, the chloroether resin includes chloroether resin MP45, and the paraffin includes No. 52 fully refined paraffin.

[0044] In some specific embodiments, if calculated by weight percentage, preferably, the addition ratio of the following components of the modified methyl methacrylate resin is as shown in Table 1.

[0045] Table 1

[0046]

[0047]

[0048] In a second aspect, based on the same inventive concept, the present invention provides a method for preparing the modified methyl methacrylate resin according to any one of the first aspects, the preparation method comprising the following steps:

[0049] In an inert gas atmosphere, methyl methacrylate monomer, n-butyl acrylate monomer and initiator are stirred and heated to 125-135° C., then kept warm and methacrylic acid monomer is added dropwise to carry out polymerization reaction, and the viscosity of the reaction system is between 45 Pa·s and 70 Pa·s to obtain a first reaction solution;

[0050] The first reaction solution is first cooled to 75-85° C., and then paraffin, chloropalm oil methyl ester, chloroether resin, polyvinyl butyral and trimethylolpropane triacrylate monomer are added and first stirred and mixed to obtain a second reaction solution;

[0051] The second reaction solution is subjected to a second cooling down to 40-50° C., and then an accelerator, a polymerization inhibitor and 2,4,6-trimethylbenzoyldiphenoxyphosphine are added thereto for a second stirring and mixing to obtain the modified methyl methacrylate resin.

[0052] In some specific embodiments, the dripping speed of the methacrylic acid monomer is 8-12 kg / h, the polymerization reaction time is 2.5-3.5 hours, the endpoint temperature of the first cooling is 80°C, and the endpoint temperature of the second cooling is 45°C.

[0053] In some specific embodiments, the working condition parameters of the first stirring and mixing include: stirring time of 1 to 2 hours, stirring speed of 100 to 200 rpm; the working condition parameters of the second stirring and mixing include: stirring time of 1 to 2 hours, stirring speed of 100 to 200 rpm.

[0054] In some specific embodiments, the preparation method of the modified methyl methacrylate resin comprises the following process:

[0055] Methyl methacrylate monomer and n-butyl acrylate monomer are placed into a 1-ton reactor through a high-level tank. Azobisisobutyronitrile initiator is added simultaneously with the two monomers and the agitator of the reactor is turned on to allow the three materials to be fully mixed.

[0056] When the monomer feeding is completed, close the feeding valve, open the nitrogen switch and the exhaust valve, fill the reactor with nitrogen and exhaust the air to reduce the inhibitory effect of oxygen on free radical polymerization during the polymerization reaction.

[0057] Confirm that the drain valve of the reactor is open, drain all the cooling water in the reactor interlayer and close the drain valve; slowly open the steam valve to heat the reactor. When the temperature in the reactor reaches 65 degrees Celsius, the azobisisobutyronitrile initiator begins to decompose, and the speed of the reactor paddle stirrer is adjusted to 140rpm. When the temperature rises to 130 degrees Celsius, close the steam valve to stop heating and maintain the temperature of 130 degrees Celsius for polymerization for about 3 hours. If the temperature rises above 140 degrees Celsius, half-open the cooling water valve to keep the temperature at around 130 degrees Celsius, and the error cannot exceed plus or minus 5 degrees Celsius; during the insulation process, add 2% of methacrylic acid by weight at a drip rate of 10kg / h.

[0058] After 3 hours of polymerization, 1L of copolymer solution of methyl methacrylate, n-butyl acrylate and methacrylic acid was taken out from the sampling valve of the reactor. The temperature of the sample was quickly reduced to 100 degrees Celsius by ice water prepared in advance and the viscosity was tested using a Stormer viscometer. When the viscosity was between 45Pa·s and 70Pa·s, the heat preservation was stopped and the cooling process was started. The cooling water outlet valve and water inlet valve of the reactor were opened in turn to cool the materials in the reactor.

[0059] When the temperature drops to 80 degrees Celsius, the following are added into the reactor: No. 52 fully refined paraffin, chloropalm oil methyl ester, chloroether resin MP45, polyvinyl butyral, and trimethylolpropane triacrylate monomer.

[0060] When the temperature drops to 45 degrees Celsius, add: dimethyl para-toluidine, dihydroxyethyl para-toluidine, dicyclopentadiene iron combined accelerator, p-diphenol monomethyl ether inhibitor and BHT compound inhibitor, 2,4,6-trimethylbenzoyl diphenoxyphosphine.

[0061] Discharge from the discharge port of the reactor and store in a 200L iron barrel. Use a 100-mesh filter to filter during discharge. The packaging specifications should give full play to the characteristics of oxygen inhibiting the polymerization of methyl methacrylate resin to extend the storage period of the resin; the packaging specification of a 200L packaging barrel is 180kg / barrel.

[0062] In a third aspect, based on the same inventive concept, the present invention provides a use of the modified methyl methacrylate resin described in any one of the first aspect and the second aspect in the preparation of a coating.

[0063] It should be noted that the components and raw materials involved in the modified methyl methacrylate resin and its preparation method and application provided in the embodiments of the present invention, unless otherwise specified or specified, can be directly commercially available products or homemade using existing public preparation methods; at the same time, the steps and parameters involved, unless otherwise specified or specified, can be carried out according to the processing technology of the prior art or directly using existing equipment, and the present invention document will not repeat them one by one.

[0064] The present invention will be further described below in conjunction with specific examples. It should be understood that these examples are intended only to illustrate the present invention and are not intended to limit the scope of the present invention. The experimental methods in the following examples that do not specify specific conditions are usually measured according to national standards. If there is no corresponding national standard, then the conditions recommended by the manufacturer are followed.

[0065] Example 1

[0066] This example provides a modified methyl methacrylate resin, which includes the following components in parts by weight:

[0067] 53 parts of methyl methacrylate monomer, 31 parts of n-butyl acrylate monomer, 2 parts of methacrylic acid monomer, 2 parts of trimethylolpropane triacrylate monomer, 4 parts of chloropalm oil methyl ester, 0.5 parts of polyvinyl butyral, 5 parts of chloroether resin, 0.5 parts of 2,4,6-trimethylbenzoyldiphenoxyphosphine, 1 part of paraffin, 0.2 parts of inhibitor, 0.02 parts of initiator, and 0.8 parts of accelerator;

[0068] The inhibitor is compounded by p-diphenol monomethyl ether and butylated hydroxytoluene in a weight ratio of 0.5:2; the promoter is compounded by N,N-dimethyl-p-toluidine, N,N-dihydroxyethyl-p-toluidine and dicyclopentadiene iron in a weight ratio of 2:6:1; the initiator is azobisisobutyronitrile, the chloroether resin is chloroether resin MP45, and the paraffin is No. 52 fully refined paraffin.

[0069] The preparation method of the modified methyl methacrylate resin comprises the following steps:

[0070] Under an inert gas atmosphere, methyl methacrylate monomer, n-butyl acrylate monomer and initiator are stirred and heated to 130° C., then kept warm and methacrylic acid monomer is added dropwise to carry out polymerization reaction. The reaction time is 3 hours, and the viscosity of the reaction system is between 45 Pa·s and 70 Pa·s, to obtain a first reaction solution;

[0071] The first reaction solution is first cooled to 80° C., and then paraffin, chloropalm oil methyl ester, chloroether resin, polyvinyl butyral and trimethylolpropane triacrylate monomer are added and first stirred and mixed for 1.5 hours at a stirring speed of 140 rpm to obtain a second reaction solution;

[0072] The second reaction solution was cooled to 45° C. for a second time, and then a promoter, a polymerization inhibitor and 2,4,6-trimethylbenzoyldiphenoxyphosphine were added for a second stirring and mixing. The stirring time was 1.5 hours and the stirring speed was 140 rpm to obtain the modified methyl methacrylate resin.

[0073] Example 2

[0074] This example provides a modified methyl methacrylate resin, which includes the following components in parts by weight:

[0075] 50 parts of methyl methacrylate monomer, 35 parts of n-butyl acrylate monomer, 1 part of methacrylic acid monomer, 3 parts of trimethylolpropane triacrylate monomer, 5 parts of chloropalm oil methyl ester, 0.3 parts of polyvinyl butyral, 5.7 parts of chloroether resin, 0.2 parts of 2,4,6-trimethylbenzoyldiphenoxyphosphine, 0.5 parts of paraffin, 0.1 parts of inhibitor, 0.05 parts of initiator, and 0.5 parts of accelerator;

[0076] The inhibitor is compounded by p-diphenol monomethyl ether and butylated hydroxytoluene in a weight ratio of 0.5:2; the promoter is compounded by N,N-dimethyl-p-toluidine, N,N-dihydroxyethyl-p-toluidine and dicyclopentadiene iron in a weight ratio of 2:6:1; the initiator is azobisisobutyronitrile, the chloroether resin is chloroether resin MP45, and the paraffin is No. 52 fully refined paraffin.

[0077] The preparation method of the modified methyl methacrylate resin is the same as that of Example 1.

[0078] Example 3

[0079] This example provides a modified methyl methacrylate resin, which includes the following components in parts by weight:

[0080] 60 parts of methyl methacrylate monomer, 25 parts of n-butyl acrylate monomer, 2 parts of methacrylic acid monomer, 2 parts of trimethylolpropane triacrylate monomer, 3 parts of chloropalm oil methyl ester, 0.8 parts of polyvinyl butyral, 3.4 parts of chloroether resin, 0.8 parts of 2,4,6-trimethylbenzoyldiphenoxyphosphine, 1.5 parts of paraffin, 0.5 parts of inhibitor, 0.03 parts of initiator, 1 part of accelerator;

[0081] The inhibitor is compounded by p-diphenol monomethyl ether and butylated hydroxytoluene in a weight ratio of 0.5:2; the promoter is compounded by N,N-dimethyl-p-toluidine, N,N-dihydroxyethyl-p-toluidine and dicyclopentadiene iron in a weight ratio of 2:6:1; the initiator is azobisisobutyronitrile, the chloroether resin is chloroether resin MP45, and the paraffin is No. 52 fully refined paraffin.

[0082] The preparation method of the modified methyl methacrylate resin is the same as that of Example 1.

[0083] Comparative Example 1

[0084] This example provides a modified methyl methacrylate resin and a preparation method thereof, which is different from Example 1 only in that no trimethylolpropane triacrylate monomer is added; the remaining steps and parameters are the same.

[0085] Comparative Example 2

[0086] This example provides a modified methyl methacrylate resin and a preparation method thereof, which is different from Example 1 only in that no chloropalm oil methyl ester is added; the remaining steps and parameters are the same.

[0087] Comparative Example 3

[0088] This example provides a modified methyl methacrylate resin and a preparation method thereof, which is different from Example 1 only in that no polyvinyl butyral is added; the remaining steps and parameters are the same.

[0089] Comparative Example 4

[0090] This example provides a modified methyl methacrylate resin and a preparation method thereof, which is different from Example 1 only in that no chloroether resin MP45 is added; the remaining steps and parameters are the same.

[0091] Comparative Example 5

[0092] This example provides a modified methyl methacrylate resin and a preparation method thereof, which is different from Example 1 only in that 2,4,6-trimethylbenzoyldiphenoxyphosphine is not added; the remaining steps and parameters are the same.

[0093] Comparative Example 6

[0094] This example provides a modified methyl methacrylate resin and a preparation method thereof, which is different from Example 1 only in that when the first reaction solution is cooled, the viscosity of the reaction system is 35 Pa·s; the remaining steps and parameters are the same.

[0095] Test Case

[0096] In this example, the modified methyl methacrylate resins obtained in the above Examples 1 to 3 and Comparative Examples 1 to 6 were subjected to performance tests.

[0097] Test method and standard: Add benzoyl peroxide (BPO) to each test sample at a ratio of 100 to 2 at an ambient temperature of 23 degrees Celsius, stir with a high-speed disperser for 1 minute to allow BPO to completely dissolve in the resin, and then make plates and test according to the corresponding methods in GB / T16777-2008, GB / T5210-2006, and GB / T2411-2008; 1) Tensile strength is based on GB / T16777-200 8, Chapter 9; 2) Elongation at break is in accordance with GB / T16777-2008, Chapter 9; 3) Adhesion to steel plate is in accordance with GB / T5210-2006; 4) Shore hardness is in accordance with GB / T2411-2008; 5) Low temperature flexibility is in accordance with GB / T16777-2008, Chapter 13; 6) Solid content is in accordance with GB / T16777-2008, Chapter 5; 7) Drying time is in accordance with GB / T16777-2008, Chapter 16.

[0098] The test results are shown in Table 2.

[0099] Table 2

[0100]

[0101] Various embodiments of the present invention may be presented in the form of a range; it should be understood that the description in the form of a range is only for convenience and brevity, and should not be understood as a rigid limitation on the scope of the present invention; therefore, the range description should be considered to have specifically disclosed all possible sub-ranges and single numerical values ​​within the range. For example, the range description from 1 to 6 should be considered to have specifically disclosed sub-ranges, such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as single numbers within the range, such as 1, 2, 3, 4, 5 and 6, which apply regardless of the range. In addition, whenever a numerical range is indicated herein, it is meant to include any cited number (fractional or integer) within the indicated range.

[0102] The foregoing is merely a specific embodiment of the present invention, which enables those skilled in the art to understand or implement the present invention. Various modifications to these embodiments will be apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the present invention. Therefore, the present invention will not be limited to the embodiments shown herein, but rather to the widest scope consistent with the principles and novel features claimed herein.

Claims

1. A modified methyl methacrylate resin, characterized in that: The modified methyl methacrylate resin comprises the following components in parts by weight: 50-60 parts of methyl methacrylate monomer, 25-35 parts of n-butyl acrylate monomer, 1-2 parts of methacrylic acid monomer, 2-3 parts of trimethylolpropane triacrylate monomer, 3-5 parts of chloropalm oil methyl ester, 0.3-0.8 parts of polyvinyl butyral, 3.4-5.7 parts of chloroether resin, 0.2-0.8 parts of 2,4,6-trimethylbenzoyldiphenoxyphosphine, 0.5-1.5 parts of paraffin, 0.1-0.5 parts of inhibitor, 0.02-0.05 parts of initiator, and 0.5-1 parts of accelerator.

2. The modified methyl methacrylate resin according to claim 1, characterized in that The modified methyl methacrylate resin comprises the following components in parts by weight: 53 parts of methyl methacrylate monomer, 31 parts of n-butyl acrylate monomer, 2 parts of methacrylic acid monomer, 2 parts of trimethylolpropane triacrylate monomer, 4 parts of chloropalm oil methyl ester, 0.5 parts of polyvinyl butyral, 5 parts of chloroether resin, 0.5 parts of 2,4,6-trimethylbenzoyldiphenoxyphosphine, 1 part of paraffin, 0.2 parts of inhibitor, 0.02 parts of initiator, and 0.8 parts of accelerator.

3. The modified methyl methacrylate resin according to claim 1, characterized in that The polymerization inhibitor is prepared by compounding p-diphenol monomethyl ether and dibutyl hydroxytoluene in a weight ratio of (0.5-1):(2-5).

4. The modified methyl methacrylate resin according to claim 1, characterized in that The initiator is an azo initiator, and the azo initiator includes azobisisobutyronitrile.

5. The modified methyl methacrylate resin according to claim 1, characterized in that The accelerator is prepared by compounding N,N-dimethyl-p-toluidine, N,N-dihydroxyethyl-p-toluidine and dicyclopentadienyl iron in a weight ratio of (1-3):(5-8):(1-2).

6. The modified methyl methacrylate resin according to claim 1, characterized in that The chloroether resin includes chloroether resin MP45, and the paraffin includes No. 52 fully refined paraffin.

7. A method for preparing the modified methyl methacrylate resin according to any one of claims 1 to 6, characterized in that: The preparation method comprises the following steps: In an inert gas atmosphere, methyl methacrylate monomer, n-butyl acrylate monomer and initiator are stirred and heated to 125-135° C., then kept warm and methacrylic acid monomer is added dropwise to carry out polymerization reaction, and the viscosity of the reaction system is between 45 Pa·s and 70 Pa·s to obtain a first reaction solution; The first reaction solution is first cooled to 75-85° C., and then paraffin, chloropalm oil methyl ester, chloroether resin, polyvinyl butyral and trimethylolpropane triacrylate monomer are added and first stirred and mixed to obtain a second reaction solution; The second reaction solution is subjected to a second cooling down to 40-50° C., and then an accelerator, a polymerization inhibitor and 2,4,6-trimethylbenzoyldiphenoxyphosphine are added thereto for a second stirring and mixing to obtain the modified methyl methacrylate resin.

8. The method for preparing the modified methyl methacrylate resin according to claim 7, characterized in that: The dropping speed of the methacrylic acid monomer is 8-12 kg / h, the polymerization reaction time is 2.5-3.5 hours, the end point temperature of the first cooling is 80° C., and the end point temperature of the second cooling is 45° C.

9. The method for preparing the modified methyl methacrylate resin according to claim 7, characterized in that: The working condition parameters of the first stirring and mixing include: stirring time of 1 to 2 hours, stirring speed of 100 to 200 rpm; the working condition parameters of the second stirring and mixing include: stirring time of 1 to 2 hours, stirring speed of 100 to 200 rpm.

10. Use of the modified methyl methacrylate resin according to any one of claims 1 to 9 in the preparation of coatings.

Images