CN115677948A - High specific gravity transparent resin composition and method for producing particles thereof - Google Patents
High specific gravity transparent resin composition and method for producing particles thereof Download PDFInfo
- Publication number
- CN115677948A CN115677948A CN202211445009.4A CN202211445009A CN115677948A CN 115677948 A CN115677948 A CN 115677948A CN 202211445009 A CN202211445009 A CN 202211445009A CN 115677948 A CN115677948 A CN 115677948A
- Authority
- CN
- China
- Prior art keywords
- transparent resin
- specific gravity
- high specific
- resin composition
- acrylate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention provides a high specific gravity transparent resin composition and a preparation method of particles thereof, wherein the preparation method of the high specific gravity transparent resin composition comprises the following steps: putting acrylic acid or (methyl) acrylic acid, pre-crushed brominated epoxy resin, a polymerization inhibitor and an antioxidant into a reaction kettle for mixing, heating to 60-70 ℃, gradually adding a reaction catalyst, maintaining the reaction temperature between 80-90 ℃ for 2-3 hours until the acid value reaches 10-20, then cooling to 65-75 ℃, adding a reactive monomer diluent, a polymerization inhibitor and a toner, and reacting to obtain the high-specific-gravity transparent resin composition. The method has the advantages that the required reaction temperature is relatively low, the brominated epoxy resin does not need to be melted at high temperature, the phenomena of easy color change, gel and the like in the melting process can be avoided, and the phenomenon of yellowing of the brominated epoxy resin caused by overheating due to uneven heating in the melting process can be avoided. The transparent particles prepared by using the high specific gravity transparent resin composition have better yellowing resistance.
Description
Technical Field
The invention relates to the technical field of acrylic resin, in particular to a high-specific-gravity transparent resin composition and a preparation method of particles thereof.
Background
The acrylic solid plane material (also called acrylic plate) is generally produced by dissolving polymethyl methacrylate resin in methyl methacrylate monomer to produce acrylate resin (commonly called acrylic resin), or by prepolymerizing methyl methacrylate monomer to produce acrylic resin with a certain solid content, then dispersing and mixing acrylic resin, aluminum hydroxide powder, color particles or transparent particles and color paste thereof, and adding solidified initiator and accelerant to form the acrylic solid plane material at normal temperature.
The acrylic solid plane material made of the transparent particles can further simulate the transparent characteristic of natural stone, and the demand for the transparent particles is gradually increased in recent years. The transparent particles are generally made of acrylic resin or unsaturated polyester resin, and the obtained acrylic solid plane material has high light transmittance, but the specific gravity of the transparent particles is only about 1.15-1.2, so the transparent particles cannot be uniformly dispersed in acrylic plate slurry, and the transparent particles usually float on the back of the plate, so the acrylic solid plane material has an effect of uneven distribution.
The high-specific-gravity transparent particles can be prepared by using high-specific-gravity transparent brominated epoxy resin, and the preparation method comprises two methods, wherein one method is disclosed by a Chinese patent with an authorization publication number of CN104945845B, the brominated epoxy resin is directly added with an amine curing agent to be cured to prepare a plate and then is crushed and granulated to form the transparent particles, and the other method is disclosed by a Chinese patent with an authorization publication number of CN101484524B, brominated epoxy acrylate resin is firstly prepared, the resin is cured by using the curing agent to prepare a transparent particle plate, and then is crushed and granulated to form the transparent particles. The brominated epoxy resin is required to be subjected to high-temperature dispersion melting in the two modes, the brominated epoxy resin is easy to discolor at high temperature, the brominated epoxy resin is uneven in heating, and is easy to discolor or even cause gel, and the defects of difficult production operation, poor safety and the like exist.
In addition, the yellowing resistance and solvent resistance of the particles prepared by the first method are insufficient, the requirement of acrylic solid plane materials on the transparent particles cannot be met, the solvent resistance of the particles can be improved by the second method, but the brominated epoxy resin is required to be melted at high temperature and prepared by a method of titrating and gradually reacting with acrylic acid, the process operation is complex, and the yellowing resistance of the transparent particles is reduced by using copper naphthenate for resin curing.
Disclosure of Invention
In view of the disadvantages of the prior art, one aspect of the present invention is to provide a method for preparing a high specific gravity transparent resin composition, which can reduce the difficulty of production operations and improve the safety of the preparation process, and the prepared high specific gravity transparent resin composition has stronger yellowing resistance.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for preparing a high specific gravity transparent resin composition, comprising the steps of:
s1: putting acrylic acid or (methyl) acrylic acid, pre-crushed brominated epoxy resin, a polymerization inhibitor and an antioxidant into a reaction kettle for mixing, and starting steam to heat until the temperature reaches 60-70 ℃;
s2: gradually adding a reaction catalyst in batches, controlling the reaction temperature between 80 and 90 ℃, and keeping the temperature for 2 to 3 hours until the acid value reaches 10 to 20;
s3: cooling to 65-75 deg.c, adding reactive monomer diluent, polymerization inhibitor and toner, and reacting to obtain transparent resin composition with number average molecular weight of 2000-4000 and high specific weight.
Preferably, the pre-ground brominated epoxy resin has an epoxy equivalent weight of 250 to 600.
Preferably, the reactive monomer diluent is one or more of methyl methacrylate, butyl methacrylate, t-butyl methacrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ethoxyethoxyethyl acrylate, epoxy acrylate of glycidyl methacrylate, 1,6-hexanediol di (meth) acrylate, glycerol tri (meth) acrylate, methylpropanediol di (meth) acrylate, polyethylene glycol di (meth) acrylate, styrene, halogenated styrene, vinyl toluene, divinylbenzene, alpha-methylstyrene dimer.
Preferably, the reaction catalyst is one or more of benzyltriethylammonium chloride, dimethylbenzylamine, di-n-butylamine, dimethylphenylbenzylamine, tetramethylammonium chloride, dimethylphenylbenzylammonium chloride, triethylamine and ethyltriphenylammonium bromide.
Preferably, the polymerization inhibitor is one or more of dibutyl hydroxy toluene, dimethyl p-benzoquinone, p-tert-butyl catechol, hydroquinone, methyl hydroquinone, hydroquinone monomethyl ether and p-benzoquinone, and the antioxidant is one or more of antioxidant 1010, antioxidant 1076, antioxidant 168, antioxidant DLTP and antioxidant DSTP.
Preferably, in the S3 step, an ultraviolet absorber and a plasticizer are added.
Preferably, the plasticizer is dimethyl phthalate, diethyl phthalate, di-n-butyl phthalate, dioctyl phthalate, butyl benzyl phthalate, di (2-ethyl) hexyl phthalate, diisononyl phthalate, diethylene glycol dibenzoate, dipropylene glycol dibenzoate, triethylene glycol dibenzoate, diethylene glycol dibenzoate, and a mixture or a dibenzoate mixture thereof, and the ultraviolet absorbent is one or more of UV-P, UV, UV326, UV327, UV531 and UV 571.
In another aspect, the present invention provides a method for preparing particles from a high specific gravity transparent resin, which comprises the following steps:
a method for preparing high specific gravity transparent resin particles, comprising the steps of:
s10: putting the high-specific-gravity transparent resin composition into a stirring cylinder, heating to 60-70 ℃, adding a peroxide initiator and a toner, uniformly stirring, and pouring into a mold;
s20: and (3) placing the die into an oven with the temperature of 70-80 ℃ for baking for 30-60 minutes, cooling and solidifying the die into a plate, and crushing the plate to obtain the high-specific-gravity transparent resin particles.
Preferably, the barbituric hardness of the board is 45 to 55.
Preferably, the peroxide initiator is one or more of dibenzoyl peroxide, diisobutyryl peroxide, cumyl peroxyneodecanoate, bis (3-methoxybutyl) peroxydicarbonate, bis (ethoxyhexyl) peroxydicarbonate, tert-amyl peroxyneodecanoate, bis (2-ethylhexyl) peroxydicarbonate, bis (4-tert-butylcyclohexyl) peroxydicarbonate, diisopropyl peroxydicarbonate, dicetyl peroxydicarbonate, tert-butyl peroxy-2-ethylhexanoate, bis (4-tert-butylcyclohexyl) peroxydicarbonate, 8978 zft 8978-tetramethylbutyl peroxypivalate and tert-amyl peroxypivalate.
Compared with the prior art, the invention has the beneficial effects that:
1. the preparation method of the brominated epoxy acrylate resin composition is changed, the dissolubility of solid brominated epoxy resin in acrylic acid or (methyl) acrylic acid is utilized, the brominated epoxy resin and the acrylic acid or (methyl) acrylic acid are directly mixed, so that the brominated epoxy resin is easy to generate addition reaction with the acrylic acid or the (methyl) acrylic acid after being dissolved, the reaction required temperature is relatively low, the brominated epoxy resin does not need to be melted at high temperature, the situations of easy color change, gel and the like in the melting process can be avoided, the production operation difficulty is reduced, the safety of the preparation process is improved, and the phenomenon that the brominated epoxy resin is yellow due to overheating caused by uneven heating in the melting process can be avoided;
2. the polymerization temperature is increased step by adding the reaction catalyst, so that the reaction is carried out at a lower temperature, the resin is prevented from yellowing caused by high temperature, and the resin is not easy to oxidize in the polymerization process without introducing nitrogen;
3. the method of curing by peroxide is adopted to prepare the high-specific-gravity transparent resin particles, so that the use of amine curing agents is avoided, and the curing temperature is low, so that the generated particles have better yellowing resistance.
Detailed Description
The invention is further illustrated by the following examples. These examples are intended to illustrate the invention and are not intended to limit the scope of the invention. Experimental procedures without specific conditions noted in the following examples, generally according to conditions conventional in the art or as recommended by the manufacturer; the raw materials, reagents and the like used are, unless otherwise specified, those commercially available from the conventional markets and the like. Any insubstantial changes and substitutions made by those skilled in the art based on the present invention are intended to be covered by the claims.
The high specific gravity transparent resin composition of each example of the present invention is prepared by the following process:
s1: putting acrylic acid or (methyl) acrylic acid, pre-crushed brominated epoxy resin, a polymerization inhibitor and an antioxidant into a reaction kettle provided with a stirring paddle, a thermometer and a jacket, and starting steam to heat until the temperature reaches 60-70 ℃; the solid brominated epoxy resin is dissolved by using acrylic acid or (methyl) acrylic acid, the brominated epoxy resin is easy to generate addition reaction with the acrylic acid or (methyl) acrylic acid after being dissolved, the temperature required by the reaction is relatively low, the brominated epoxy resin does not need to be melted at high temperature, the phenomena of easy color change, easy gelation and the like in the melting process can be avoided, the production operation difficulty is reduced, the safety of the preparation process is improved, and the phenomenon of yellowing caused by overheating due to uneven heating in the melting process of the brominated epoxy resin can be avoided;
s2: gradually adding a reaction catalyst in batches, controlling the reaction temperature between 80 and 90 ℃, and keeping the temperature for 2 to 3 hours until the acid value reaches 10 to 20; the polymerization temperature is controlled by adding the reaction catalyst step by step, so that the reaction is carried out at a lower temperature, resin yellowing caused by high temperature is avoided, and the resin is not easy to oxidize in the polymerization process without introducing nitrogen.
S3: cooling to 65-75 deg.c, maintaining the temperature, adding reactive monomer diluent, polymerization inhibitor, toner, ultraviolet ray absorber and plasticizer to produce high specific weight transparent brominated epoxy acrylate resin composition with number average molecular weight of 2000-4000. The brominated epoxy acrylate resin has a specific gravity similar to that of acrylic plate slurry and has high transparency characteristics, and also has sanding property and hardness similar to that of acrylic plates and good compatibility with acrylic resin.
Wherein, the epoxy equivalent of the brominated epoxy resin is 250-600;
the polymerization inhibitor can be one or more of dibutyl hydroxy toluene (BHT), dimethyl p-benzoquinone, p-tert-butyl catechol, hydroquinone, methyl hydroquinone, hydroquinone monomethyl ether and p-benzoquinone;
the antioxidant can be one or more of antioxidant 1010, antioxidant 1076, phosphorous acid or phosphide antioxidant 168, antioxidant DLTP, and antioxidant DSTP;
the reaction catalyst can be one or more of benzyltriethylammonium chloride, dimethylbenzylamine, di-n-butylamine, dimethylphenylbenzylamine, tetramethylammonium chloride, dimethylphenylbenzylammonium chloride, triethylamine and ethyltriphenylammonium bromide;
the ultraviolet absorbent can be one or more of 2- (2 '-hydroxy-5' -methylphenyl) benzotriazole (UV-P), 2- (2 '-hydroxy-3', 5 '-dipentylphenyl) benzotriazole (UV 328), 2- (2' -hydroxy-3 '-tert-butyl-5' -methylphenyl) -5-chlorobenzotriazole (UV 326/327), 2-hydroxy-4-n-octoxybenzophenone (UV 531) and 2- (2H-benzotriazole-2-yl) -6- (dodecyl) -4-methylphenol (UV 571);
the plasticizer may be selected from dimethyl phthalate (DMP), diethyl phthalate (DEP), di-n-butyl phthalate (DBP), dioctyl phthalate (DOP), butyl Benzyl Phthalate (BBP), di-2-ethyl hexyl phthalate (DEHP), diisononyl phthalate (DINP), diethylene glycol dibenzoate, dipropylene glycol dibenzoate, triethylene glycol dibenzoate, diethylene glycol dibenzoate, and mixtures thereof or mixtures thereof; the plasticizer is added in a certain amount to control the toughness of the high specific gravity transparent resin composition cured plate, so that fine powder is not easy to generate in the plate crushing process, and the utilization rate of particles is improved. After the resin without the plasticizer is solidified into the plate, the utilization rate of the particles obtained by crushing the plate is 50-60%, and after the resin with the plasticizer is solidified into the plate, the utilization rate of the particles obtained by crushing the plate is more than 85%.
The reactive monomer diluent may be selected from the group consisting of methyl methacrylate, butyl methacrylate, t-butyl methacrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ethoxyethoxyethyl acrylate, epoxy acrylate of glycidyl methacrylate, 1,6-hexanediol di (meth) acrylate, glycerol tri (meth) acrylate, methylpropanediol di (meth) acrylate, polyethylene glycol di (meth) acrylate, styrene, halogenated styrene, vinyl toluene, divinylbenzene, alpha-methylstyrene dimer, and mixtures thereof;
phosphorous acid or phosphide can be used as the toner.
The process of preparing the pellets using the high specific gravity transparent resin composition according to the embodiments of the present invention is as follows:
adding the high specific gravity transparent resin composition into a stirring cylinder, heating to 60-70 ℃, then adding a peroxide initiator and a toner, uniformly stirring, pouring into a 304 stainless steel mold, placing into a 70-80 ℃ oven, baking for 30-60 minutes, cooling and solidifying into a plate, and crushing into high specific gravity transparent particles when the Babbitt hardness reaches 45-55, wherein the high specific gravity transparent particles are used for manufacturing acrylic solid plane materials. The curing temperature of 70-80 ℃ is lower, and yellowing can be avoided.
Wherein the peroxide initiator can be one or more of dibenzoyl peroxide, diisobutyryl peroxide, cumyl peroxyneodecanoate, bis (3-methoxybutyl) peroxydicarbonate, bis (ethoxyhexyl) peroxydicarbonate, tert-amyl peroxyneodecanoate, bis (2-ethylhexyl) peroxydicarbonate, bis (4-tert-butylcyclohexyl) peroxydicarbonate, diisopropyl peroxydicarbonate, dicetyl peroxydicarbonate, tert-butyl peroxy-2-ethylhexanoate, bis (4-tert-butylcyclohexyl) peroxydicarbonate, 8978 zft 8978-tetramethylbutyl peroxypivalate and tert-amyl peroxypivalate; and by using a peroxide initiator, an amine curing agent is not used, so that the high-specific-gravity transparent particles have better yellowing resistance.
The toner may be selected from phosphorous acid or phosphide.
Example 1
Preparation of a high specific gravity transparent resin composition:
charging 100 parts by weight of (meth) acrylic acid, 0.25 parts by weight of polymerization inhibitor methylhydroquinone and 0.25 parts by weight of antioxidant 1010 into a 1000 liter reaction vessel equipped with a stirring paddle, a thermometer and a jacket, followed by charging pre-pulverized 350 parts by weight of brominated epoxy resin having an epoxy equivalent of about 400 and heating the material to 70 ℃ with controlled steam;
gradually adding 1 weight part of reaction catalyst dimethylphenylbenzylamine in batches for ten times in one hour, controlling the reaction temperature to be between 80 and 90 ℃, keeping the temperature for 150 minutes, measuring the acid value of a material to be 15, and cooling to 69 ℃ after the reaction is finished;
to the cooled reaction product were added 40 parts by weight of methyl methacrylate as a reactive monomer diluent, 1.25 parts by weight of dibutylhydroxytoluene (BHT) as a polymerization inhibitor, 0.05 parts by weight of a toner, 2.5 parts by weight of an ultraviolet absorber UV-P, and 25 parts by weight of triethylene glycol dibenzoate as a plasticizer, and reacted to give a high specific gravity transparent brominated epoxy acrylate resin composition, the viscosity of which was measured to be 950CPS.
Preparing high specific gravity transparent particles:
adding 20 parts by weight of the high-specific-gravity transparent resin composition into a stirring cylinder, heating to 60-70 ℃, adding 0.2 part by weight of dibenzoyl peroxide initiator and 0.01 part by weight of toner, uniformly stirring, pouring into a 304 stainless steel mold, baking for 60 minutes in a 75 ℃ oven, curing to obtain the plate, cooling to obtain 52 Babbitt hardness, and crushing to obtain the high-specific-gravity transparent particles for acrylic solid plane materials with various meshes.
Example 2
Preparation of a high specific gravity transparent resin composition:
introducing 90 parts by weight of acrylic acid, 0.25 parts by weight of Butylated Hydroxytoluene (BHT) as polymerization inhibitor and 0.25 parts by weight of antioxidant 1076 into a 1000 liter reaction vessel equipped with a stirring paddle, a thermometer and a jacket, then introducing 350 parts by weight of a pre-pulverized brominated epoxy resin having an epoxy equivalent of about 350 and controlling steam to heat the material to 70 ℃;
gradually adding 1.1 weight parts of reaction catalyst benzyltriethylammonium chloride in batches for ten times within one hour, controlling the reaction temperature to be between 80 and 90 ℃, keeping the temperature for 160 minutes, measuring the acid value of a material to be 12, and cooling to 70 ℃ after the reaction is finished;
to the cooled reaction product were added 4 parts by weight of methyl methacrylate as a reactive monomer diluent, 4 parts by weight of styrene as a reactive monomer diluent, 0.25 part by weight of dibutylhydroxytoluene (BHT) as a polymerization inhibitor, 0.01 part by weight of a toner, 0.5 part by weight of an ultraviolet absorber UV-328, and 3 parts by weight of a plasticizer dibenzoate mixture, and reacted to produce a brominated epoxy acrylate resin composition having a viscosity of 850CPS.
Preparing high specific gravity transparent particles:
adding 20 parts by weight of the high-specific-gravity transparent resin composition into a stirring cylinder, heating to 60-70 ℃, then adding 0.1 part by weight of dibenzoyl peroxide, 0.05 part by weight of bis (2-ethylhexyl) peroxydicarbonate initiator and 0.002 part by weight of toner, uniformly stirring, pouring into a 304 stainless steel mold, putting into a 75 ℃ oven, baking for 50 minutes, curing into a plate, cooling, and crushing into high-specific-gravity transparent particles for acrylic solid plane materials with various meshes, wherein the Babbitt hardness of the plate reaches 50.
Example 3
Preparation of a high specific gravity transparent resin composition:
charging 100 parts by weight of (meth) acrylic acid, 0.25 parts by weight of inhibitor dibutylhydroxytoluene (BHT) and 0.25 parts by weight of antioxidant 168 into a 1000 liter reaction vessel equipped with a stirring paddle, a thermometer and a jacket, followed by addition of pre-pulverized 350 parts by weight of brominated epoxy resin having an epoxy equivalent of about 400 and controlled steam to heat the batch to 60 ℃;
gradually adding 1.1 weight parts of dimethyl phenyl benzyl ammonium chloride reaction catalyst into the mixture in batches for ten times within one hour, controlling the reaction temperature to be between 80 and 90 ℃, keeping the temperature for 140 minutes, measuring the acid value of a material to be 11, and cooling the material to 65 ℃ after the reaction is finished;
to the cooled reaction product were added 45 parts by weight of styrene, a reactive monomer diluent, 1.25 parts by weight of dibutylhydroxytoluene (BHT), a polymerization inhibitor, 0.05 parts by weight of a toner, 2.5 parts by weight of an ultraviolet absorber UV-327, and 15 parts by weight of a plasticizer dibenzoate mixture, and reacted to produce a brominated epoxy acrylate resin composition, and the viscosity of the composition was measured to be 1000CPS.
Preparing high specific gravity transparent particles:
adding 20 parts by weight of the brominated epoxy acrylate resin composition into a stirring cylinder, heating to 60-70 ℃, then adding 0.05 part by weight of dibenzoyl peroxide, 0.05 part by weight of bis (4-tert-butylcyclohexyl) peroxydicarbonate mixed initiator and 0.05 part by weight of toner, uniformly stirring, pouring into a 304 stainless steel mold, putting into a 70 ℃ oven, baking for 60 minutes, curing into a plate, cooling, and crushing into acrylic solid plane material high-specific-gravity transparent particles with various meshes when the Babbitt hardness reaches 49.
Comparative example 1
Preparation of a high specific gravity transparent resin composition:
the same procedure as in example 3 for preparing a high specific gravity transparent resin composition, except that no plasticizer was added, gave a brominated epoxy acrylate resin composition having an acid value of 11, and the viscosity of the composition was measured to be 900CPS.
Preparing high specific gravity transparent particles:
adding 20 parts by weight of the brominated epoxy acrylate resin composition into a stirring cylinder, heating to 60-70 ℃, then adding 0.05 part by weight of dibenzoyl peroxide, 0.05 part by weight of bis (4-tert-butylcyclohexyl) peroxydicarbonate mixed initiator and 0.05 part by weight of toner, uniformly stirring, pouring into a 304 stainless steel mold, putting into a 70 ℃ oven, baking for 60 minutes, curing into a plate, cooling, and crushing into acrylic solid plane material high-specific-gravity transparent particles with various meshes when the Babbitt hardness reaches 53.
Comparative example 2
Preparation of a high specific gravity transparent resin composition:
charging pre-pulverized 350 parts by weight of brominated epoxy resin having an epoxy equivalent of about 400 into a 1000 liter reaction vessel equipped with a stirring paddle, a thermometer and a jacket, steam heating the material to 100 ℃ until the resin is melted to a liquid state, adding 0.25 part by weight of polymerization inhibitor methylhydroquinone and 0.25 part by weight of antioxidant 1010, then starting dropwise addition of a mixed solution (the mixed solution is prepared by reacting (meth) acrylic acid with dimethylbenzylamine as a catalyst) within 3 hours, controlling the reaction temperature between 80 and 90 ℃ and maintaining the temperature for 150 minutes, measuring the acid value of the material 15, and cooling to 70 ℃ after the reaction is finished;
to the cooled reaction product were added 50 parts by weight of methyl methacrylate as a reactive monomer diluent, 1.25 parts by weight of dibutylhydroxytoluene (BHT) as a polymerization inhibitor, 0.05 parts by weight of a toner, and 2.5 parts by weight of an ultraviolet absorber UV-P, and reacted to give a high specific gravity transparent brominated epoxy acrylate resin composition having a viscosity of 800CPS.
Preparing high specific gravity transparent particles:
adding 20 parts by weight of brominated epoxy acrylate resin composition into a stirring cylinder, heating to 60-70 ℃, then adding 0.25 part by weight of dibenzoyl peroxide initiator and 0.002 part by weight of toner, uniformly stirring, pouring into a 304 stainless steel mold, placing into a 75 ℃ oven for curing for 60 minutes, cooling the cured plate to obtain acrylic solid surface material high-specific-gravity transparent particles with the Babbitt hardness of 52, and crushing into various meshes of acrylic solid surface material.
The transparent particles of each example and comparative example were measured for their properties and the results are shown in Table 1.
TABLE 1 results of Performance test of each example and comparative example
| Performance of | Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 |
| Specific gravity of | 1.585 | 1.59 | 1.578 | 1.581 | 1.576 |
| Compatibility and binding force of hot bending particles | Good taste | Good taste | Good taste | Is preferably used | Is preferably used |
| Solvent-resistant methyl methacrylate | Good taste | Good taste | Good taste | Is preferably used | In general |
| Resistance to yellowing-Total color Difference | 1.5 | 1.3 | 1.8 | 1.8 | 3.2 |
| Particle utilization ratio (8 mesh) | 85.8％ | 87.1％ | 86.4％ | 53％ | 56％ |
| Rate of fine powder of granule (over 100 mesh) | 8.6％ | 8.6％ | 9％ | 25％ | 27％ |
| Flatness of particles | Good taste | Good taste | Good taste | Good taste | Good taste |
| Babbitt hardness of the granules | 52 | 50 | 49 | 53 | 52 |
According to the test result, the method for preparing the brominated epoxy acrylate resin has the advantages that the obtained particles have better yellowing resistance and solvent resistance, the brittleness of the crushed transparent particles can be effectively controlled, and the utilization rate of the particles in the crushing process is higher.
The performance index was tested according to the following requirements:
specific gravity: measuring in an environment of 25 ℃ by using a pycnometer;
compatibility and binding force of hot-bent particles: evaluating the dispersion condition of the particles in the acrylic plate slurry;
solvent resistance: the evaluation is carried out after the glass is immersed in a solvent such as methyl methacrylate for 24 hours in an environment of 25 ℃;
yellowing resistance (200 hours xenon arc): testing according to GB/T16422.2, ISO4892-2 standard;
particle utilization (8 mesh): testing the specific gravity of the crushed 8-mesh particles;
fine particle fraction (100 mesh or more): testing the specific gravity of the crushed particles with the particle size of more than 100 meshes;
flatness of the particles: carrying out flatness evaluation on the particles polished by the 400-mesh sieve;
the Babbitt hardness of the particles: testing was performed according to ASTM D2583.
Claims (10)
1. A method for preparing a high specific gravity transparent resin composition, comprising the steps of:
s1: putting acrylic acid or (methyl) acrylic acid, pre-crushed brominated epoxy resin, a polymerization inhibitor and an antioxidant into a reaction kettle for mixing, and starting steam to heat until the temperature reaches 60-70 ℃;
s2: gradually adding a reaction catalyst in batches, controlling the reaction temperature between 80 and 90 ℃, and keeping the temperature for 2 to 3 hours until the acid value reaches 10 to 20;
s3: cooling to 65-75 deg.c, adding reactive monomer diluent, polymerization inhibitor and toner, and reacting to obtain the high specific weight transparent resin composition with number average molecular weight of 2000-4000.
2. The method for preparing a high specific gravity transparent resin composition according to claim 1, wherein: the epoxy equivalent of the pre-pulverized brominated epoxy resin is 250 to 600.
3. The method for preparing a high specific gravity transparent resin composition according to claim 2, wherein: the reactive monomer diluent is one or more of methyl methacrylate, butyl methacrylate, tert-butyl methacrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ethoxyethoxyethyl acrylate, glycidyl methacrylate epoxy acrylate, 1,6-hexanediol di (meth) acrylate, glycerol tri (meth) acrylate, methylpropanediol di (meth) acrylate, polyethylene glycol di (meth) acrylate, styrene, halogenated styrene, vinyl toluene, divinylbenzene, alpha-methyl styrene, and alpha-methyl styrene dimer.
4. The method for preparing a high specific gravity transparent resin composition according to claim 2, wherein: the reaction catalyst is one or more of benzyltriethylammonium chloride, dimethylbenzylamine, di-n-butylamine, dimethylphenylbenzylamine, tetramethylammonium chloride, dimethylphenylbenzylammonium chloride, triethylamine and ethyltriphenylammonium bromide.
5. The method for preparing a high specific gravity transparent resin composition according to claim 2, wherein: the polymerization inhibitor is one or more of dibutyl hydroxy toluene, dimethyl p-benzoquinone, p-tert-butyl catechol, hydroquinone, methyl hydroquinone, hydroquinone monomethyl ether and p-benzoquinone, and the antioxidant is one or more of antioxidant 1010, antioxidant 1076, antioxidant 168, antioxidant DLTP and antioxidant DSTP.
6. The method for preparing a high specific gravity transparent resin composition according to claim 1, wherein: in the step S3, an ultraviolet absorber and a plasticizer are added.
7. The method for preparing a high specific gravity transparent resin composition according to claim 6, wherein: the plasticizer is dimethyl phthalate, diethyl phthalate, di-n-butyl phthalate, dioctyl phthalate, butyl benzyl phthalate, di (2-ethyl) hexyl phthalate, diisononyl phthalate, diethylene glycol dibenzoate, dipropylene glycol dibenzoate, triethylene glycol dibenzoate, diethylene glycol dibenzoate and a mixture or a dibenzoate mixture thereof, and the ultraviolet absorbent is one or more of UV-P, UV, UV326, UV327, UV531 and UV 571.
8. A method for preparing high specific gravity transparent resin particles is characterized by comprising the following steps:
s10: taking the high specific gravity transparent resin composition of any one of claims 1 to 7, putting the composition into a stirring cylinder, heating the composition to 60 to 70 ℃, adding a peroxide initiator and a toner, uniformly stirring, and pouring the mixture into a mold;
s20: and (3) placing the die into an oven with the temperature of 70-80 ℃ for baking for 30-60 minutes, cooling and solidifying the die into a plate, and crushing the plate to obtain the high-specific-gravity transparent resin particles.
9. The method for preparing high specific gravity transparent resin particles according to claim 8, characterized in that: the Babbitt hardness of the plate is 45-55.
10. The method for producing high specific gravity transparent resin particles according to claim 8 or 9, characterized in that: the peroxide initiator is one or more of dibenzoyl peroxide, diisobutyryl peroxide, cumyl peroxyneodecanoate, bis (3-methoxybutyl) peroxydicarbonate, bis (ethoxyhexyl) peroxydicarbonate, tert-amyl peroxyneodecanoate, bis (2-ethylhexyl) peroxydicarbonate, bis (4-tert-butylcyclohexyl) peroxydicarbonate, diisopropyl peroxydicarbonate, dicetyl peroxydicarbonate, tert-butyl peroxy-2-ethylhexanoate, bis (4-tert-butylcyclohexyl) peroxydicarbonate, 1,1,3,3-tetramethylbutyl peroxypivalate and tert-amyl peroxypivalate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211445009.4A CN115677948B (en) | 2022-11-18 | 2022-11-18 | High specific gravity transparent resin composition and method for preparing particles thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211445009.4A CN115677948B (en) | 2022-11-18 | 2022-11-18 | High specific gravity transparent resin composition and method for preparing particles thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115677948A true CN115677948A (en) | 2023-02-03 |
| CN115677948B CN115677948B (en) | 2023-09-22 |
Family
ID=85053579
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211445009.4A Active CN115677948B (en) | 2022-11-18 | 2022-11-18 | High specific gravity transparent resin composition and method for preparing particles thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115677948B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5215863A (en) * | 1987-12-18 | 1993-06-01 | Nippon Kayaku Kabushiki Kaisha | Resin composition and solder resist composition |
| KR970042649A (en) * | 1995-12-29 | 1997-07-24 | 김충세 | Method for producing vinyl ester resin for onyx marble production. |
| JP2002138121A (en) * | 2000-11-06 | 2002-05-14 | Japan U-Pica Co Ltd | Thermosetting resin composition and artificial marble using the same |
| US20050256278A1 (en) * | 2004-05-14 | 2005-11-17 | Crump L S | Tack-free low VOC vinylester resin and uses thereof |
| CN102604000A (en) * | 2012-03-26 | 2012-07-25 | 华东理工大学华昌聚合物有限公司 | Synthetic method and application of epoxy vinyl ester resin with high bromine content |
| CN111825813A (en) * | 2020-08-07 | 2020-10-27 | 广东晨宝复合材料股份有限公司 | UV resin for quickly repairing asphalt pavement and preparation method thereof |
-
2022
- 2022-11-18 CN CN202211445009.4A patent/CN115677948B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5215863A (en) * | 1987-12-18 | 1993-06-01 | Nippon Kayaku Kabushiki Kaisha | Resin composition and solder resist composition |
| KR970042649A (en) * | 1995-12-29 | 1997-07-24 | 김충세 | Method for producing vinyl ester resin for onyx marble production. |
| JP2002138121A (en) * | 2000-11-06 | 2002-05-14 | Japan U-Pica Co Ltd | Thermosetting resin composition and artificial marble using the same |
| US20050256278A1 (en) * | 2004-05-14 | 2005-11-17 | Crump L S | Tack-free low VOC vinylester resin and uses thereof |
| CN102604000A (en) * | 2012-03-26 | 2012-07-25 | 华东理工大学华昌聚合物有限公司 | Synthetic method and application of epoxy vinyl ester resin with high bromine content |
| CN111825813A (en) * | 2020-08-07 | 2020-10-27 | 广东晨宝复合材料股份有限公司 | UV resin for quickly repairing asphalt pavement and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115677948B (en) | 2023-09-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4377055B2 (en) | Acrylic premix, acrylic artificial marble, and manufacturing method thereof | |
| US8927625B2 (en) | Resin syrup, artificial marble containing a hardened form of the resin syrup, and a production method for the same | |
| JP2009544793A (en) | Method for producing resin composition for artificial marble chip having high specific gravity and high refractive index | |
| CN112004843A (en) | Composition having excellent curability | |
| JPH0251550A (en) | Artificial stone molding | |
| CN115677948B (en) | High specific gravity transparent resin composition and method for preparing particles thereof | |
| US5164425A (en) | Artificial marble composition | |
| JPH02160648A (en) | Composition for molding polymethacrylate-based artificial marble | |
| US20090076205A1 (en) | Preparation method of small particle sized polybutadiene latex used for the production of ABS | |
| KR100383254B1 (en) | Preparation method of vinyl ester resin for preparation of onyx marble | |
| CN104710577B (en) | A kind of rostone manufacturing rostone hydroxy acrylate emulsion, preparation method and make | |
| JPH05330884A (en) | Unsaturated polyester resin composition for scagliola | |
| JP3072052B2 (en) | (Meth) acrylic molding material and method for producing the same | |
| KR101409467B1 (en) | Polymeric beads having a good thermal stability in the high temperature conditions | |
| KR101443844B1 (en) | Method for preparing vinyl chloride based resin having superior heat-resistance | |
| JP2022098813A (en) | Curable resin composition, cured product of the same and artificial marble | |
| KR101068119B1 (en) | Manufacturing Method of Composition using Marble Chip | |
| CN110734514A (en) | transparent flame-retardant polyunsaturated phosphate and preparation method thereof | |
| JPH041762B2 (en) | ||
| CN109400857A (en) | A kind of soft unsaturated polyester resin and preparation method thereof for furniture industry | |
| JP3401912B2 (en) | Method for producing unsaturated polyester resin composition and artificial marble molding | |
| JPH0912823A (en) | Synthetic resin molding material and production of molding from the same | |
| JPS6330511A (en) | Methacrylic resin molding material | |
| JPH0967447A (en) | Low profile agent for artificial marble molding, artificial marble molding produced by using the same and production of the same molding | |
| JP3178927B2 (en) | Room temperature curable resin composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |