CN109054270A - A kind of modified poly (methyl methacrylate) composition and preparation method thereof, application - Google Patents
A kind of modified poly (methyl methacrylate) composition and preparation method thereof, application Download PDFInfo
- Publication number
- CN109054270A CN109054270A CN201810749743.7A CN201810749743A CN109054270A CN 109054270 A CN109054270 A CN 109054270A CN 201810749743 A CN201810749743 A CN 201810749743A CN 109054270 A CN109054270 A CN 109054270A
- Authority
- CN
- China
- Prior art keywords
- methyl methacrylate
- core
- composition
- modified poly
- methacrylate
- 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
Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02C—SPECTACLES; SUNGLASSES OR GOGGLES INSOFAR AS THEY HAVE THE SAME FEATURES AS SPECTACLES; CONTACT LENSES
- G02C5/00—Constructions of non-optical parts
- G02C5/008—Spectacles frames characterized by their material, material structure and material properties
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
- C08L33/12—Homopolymers or copolymers of methyl methacrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/53—Core-shell polymer
Landscapes
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- General Physics & Mathematics (AREA)
- Ophthalmology & Optometry (AREA)
- Optics & Photonics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Graft Or Block Polymers (AREA)
Abstract
The present invention relates to Material Fields, and in particular to arrives a kind of modified poly (methyl methacrylate) composition and preparation method thereof, application.A kind of modified poly (methyl methacrylate) composition includes at least following components: 40~80 parts of polymethyl methacrylate, 10~65 parts of core-shell copolymerized object by weight.
Description
Technical field
The present invention relates to Material Fields, and in particular to arrives a kind of modified poly (methyl methacrylate) composition and its preparation
Method, application.
Background technique
Currently, China is the maximum glasses production in the whole world and exported country.Currently used for making the special-purpose board of high-end glasses
Material is " cellulose acetate " material (calling " acetic acid " in the following text)." acetic acid " because its dimension stability is poor, product is also easy to produce
The problems such as " warpage ", in high humility, the biggish environment of the temperature difference, product is more prone to produce deformation.Eye of the acetic acid plate in production
Before mirror, baking material is needed 72 hours to restore the dimensional structure of plate, in process of production because of poor dimensional stability, ophthalmic articles are needed
Before producing " strong frame ", therefore lead to high cost and high rework rate.The glasses finished product of acetic acid board making is also because of poor size
Stability, phenomena such as being also easy to produce distortion, deform, so as to cause " circle is read " when configuring eyeglass, error is larger, need to heat again
Eyeglass is prepared again after " whole frame ".
And traditional PMMA material, because of material shortage toughness, with the plate that PMMA makes meet the processing of glasses production with
Technique requirement.In processing, because material " brittleness " can not be carried out lathe " milling is enclosed ", finishing impression by production requirement.In heating " in pressure
In the techniques such as " face is curved " and " curved spleen ", " brittle failure " phenomenon can also occur for beam ".
In view of the above technical problems, the present invention provides a kind of dedicated modified PMMA plate of glasses, good toughness and
With the high grade of transparency, high-luster.It can satisfy the production work of plate glasses using the plate that modified PMMA of the invention makes
Skill and processing request.
Summary of the invention
In order to solve the above-mentioned technical problem, the first aspect of the invention provides a kind of modified poly (methyl methacrylate)
Composition includes at least following components: 40~80 parts of polymethyl methacrylate, core-shell copolymerized object 10~65 by weight
Part.
In a preferred embodiment, the modified poly (methyl methacrylate) composition, by weight, until
It less include following components: 50~65 parts of polymethyl methacrylate, 30~60 parts of core-shell copolymerized object.
In a preferred embodiment, the raw material for preparing of the core-shell copolymerized object is selected from acrylate and its derivative
Object, methacrylate and its derivative, butadiene and its derivative, Styrene and its derivatives, acrylonitrile and its derivative
At least one of.
In a preferred embodiment, the core-shell copolymerized object is selected from (methyl methacrylate-methacrylic acid
Butyl ester-styrene) core-shell copolymerized object, (methyl methacrylate-butyl methacrylate-butadiene) core-shell copolymerized object, methyl
Methylacrylate-butadiene-styrol copolymer, acrylonitrile-butadiene-styrene copolymer, polystyrene-polybutadiene-
Polystyrene block copolymer or polystyrene-polybutadiene-polymethylmethacrylablock block copolymer, siloxane-methyl
At least one of acrylic acid methyl copolymer, Plastoid B.
In a preferred embodiment, the core-shell copolymerized object is (methyl methacrylate-methacrylic acid fourth
Ester-styrene) core-shell copolymerized object and (methyl methacrylate-butyl methacrylate-butadiene) core-shell copolymerized object mixing
Object, wherein (methyl methacrylate-butyl methacrylate-styrene) core-shell copolymerized object and (methyl methacrylate-methyl
Butyl acrylate-butadiene) mass ratio of core-shell copolymerized object is 1.75~3.5:1.
In a preferred embodiment, the modified poly (methyl methacrylate) composition further includes 2~10 parts
Modified manometer silicon dioxide.
In a preferred embodiment, by weight, the modified poly (methyl methacrylate) composition is also
Auxiliary agent including 0.1~5 parts by weight.
In a preferred embodiment, the auxiliary agent is selected from antioxidant, light stabilizer, ultraviolet absorber, lubrication
At least one of agent, colorant.
In a preferred embodiment, the preparation method of the modified poly (methyl methacrylate) composition, until
Less the following steps are included:
By weight, high speed mixer is added the raw material into be mixed, temperature be 10~40 DEG C, revolving speed be 200~
It is transferred into circulating baking oven after 500rpm, 90~180s, handles 1~3h at 80 DEG C, is then put into twin-screw and squeezed
Out in machine, extruding pelletization under conditions of 190~220 DEG C, by obtained particle by hoisting type homogenizing bin at 70~90 DEG C
20~40min of lower homogenizing obtains the modified poly (methyl methacrylate) composition.
In a preferred embodiment, the modified poly (methyl methacrylate) composition is in manufacture optical device
In purposes, the optical device is preferably board of glasses.
The above-mentioned of the application and other features, aspects and advantages are more readily understood with reference to following detailed description.
Detailed description of the invention
Fig. 1 be dimensional stability test in circulating temperature and relative humidity variations curve, wherein "-" indicate temperature with
The change curve of time, " -- " indicate humidity with the change curve of time.
Specific embodiment
In order to solve the above-mentioned technical problem, the first aspect of the invention provides a kind of modified poly (methyl methacrylate)
Composition includes at least following components: 40~80 parts of polymethyl methacrylate, core-shell copolymerized object 10~65 by weight
Part.
In a preferred embodiment, the modified poly (methyl methacrylate) composition, by weight, until
It less include following components: 50~65 parts of polymethyl methacrylate, 30~60 parts of core-shell copolymerized object.
Polymethyl methacrylate
Polymethyl methacrylate, abbreviation PMMA are most important optical materials, have excellent comprehensive performance, excellent
Optical property and weather resistance etc..Specific performance introduction is as follows: (1) the excellent transparency, PMMA almost can be with optics
Glass compares favourably, no color, hardly picks up the full wave light of visible light, and ultraviolet light can even be penetrated to 270nm.(2) color
It adjusts colorful, because the tinctorial property of PMMA is especially good, from transparent, translucent to opaque, is ok from light color to dark color
The case where obtaining extensive tone, and hardly happening discoloration in heating or natural exposing or fade.(3) surface light
Damp good, refractive index 1.49, surface reflectivity is not more than 4%, and has graceful gloss.(4) light and tough, PMMA's
Density is 1.19g/cm3, the only half of unorganic glass, but its obdurability is suitable with inorganic strengthened glass.(5) processing and forming
Functional, material has thermoplasticity, almost can be processed into any shape.Make it that there is mobility and heat-resisting in forming material
Property several grades for combining, and can be cut off, turning, perforation, engraving, the machining such as grinding.In addition, for viscous
The various processing methods such as knot, coating, printing, dyeing are also all suitable.(6) chemical resistance is good, and PMMA can be resistance to resistance to strong acid
Highly basic, and hardly corroded by inorganic salts.In addition to this, also resistance to organic salt, grease type, aliphatic hydrocarbon
Deng.(7) weatherability is excellent, and PMMA can be used in outdoor prolonged exposure, and its mechanical property hardly declines.(8)
The mechanical property of PMMA is in medium level, obtains biaxially oriented sheet material by the stretching of orientation, mechanical property obtain compared with
Big raising.
Other than advantage of the PMMA more than possess, while there is also many shortcomings: (1) surface hardness compared with
It is low, easily scratch.(2) static behaviour is stronger, and PMMA electrical insulating property is higher, easily charges, easy dust suction, and then destroy beauty.(3) it is heated
Or expansion is easy after water suction, since the thermal expansion coefficient of PMMA is about 10 times of metal, balance water imbibition is about 2%,
And hygroscopicity linear expansion coefficient is 0.4%, and therefore, PMMA telescopic variation caused by temperature and humidity is larger.(4) elasticity of PMMA
Modulus is smaller, and elasticity modulus is only the 1/70 of iron.(5) notch sensitivity is higher, and PMMA homopolymer is more sensitive to notch,
Cracking is easy under the action of stress.(6) PMMA is easy to be corroded by certain solvents, such as in ketone, chlorohydrocarbon, aromatic hydrocarbons, esters equal solvent
In easily be dissolved etch；It can be swollen in alcohol, chlorohydrocarbon.When being contacted with above-mentioned solvent, it is easy to crack phenomenon occur.
(7) PMMA is flammable, and ignition point is about 400 DEG C, smoulder after ignition.
Polymethyl methacrylate of the invention is commercial product, is the product that the LG company trade mark is IF850.
The modification of organic glass is exactly to carry out certain adjustment and change to the structure of polymer, to make the certain of high polymer
Performance is improved and improves.It is mainly three layer of structure for being conceived to it that it, which is modified work, i.e., by changing high polymer
Molecular chain structure, aggregated structure and surface are modified to achieve the purpose that.The modification of PMMA, which is concentrated mainly on, enhances its toughness.
The toughening of polymer is exactly that the fracture mode of polymer is changed into ductile rupture by brittle fracture, is being stretched polymer
When have higher elongation at break, it is survivable when being impacted by the elongation at break impacted, also can once destroying
Absorb more energy to failure.The method of modifying that can be used at present includes copolymerization toughening, incorporation second phase particles blending toughening, adopts
With interpenetrating polymer networks structure, using biaxial oriented stretch and MULTILAYER COMPOSITE technique, fiber reinforcement technology.
Mixing second phase particles is one of important form and the most important approach of plastic toughening of blending and modifying.Second
The mode of phase particle incorporation polymer can be to be directly generated by reaction in-situ, can also be by specific structure well prepared in advance
Example be blended with polymer machinery, or the particle prepared is directly incorporated into reaction monomers, then carries out polymerizeing simultaneously anti-
It answers.For organic glass, the second phase particles generally used is rubber particles, core-shell particles, inorganic microfine particles etc..
Contact phase between second phase particles and plastic substrate is close with certain thickness, structure and polymeric matrix
And have the cenotype of significant difference with second phase particles, referred to as boundary layer.The formation of boundary layer is divided into two stages: the first stage is
Contact and impregnation process of the matrix with second phase particles.Since second phase particles are to each component in polymeric matrix or molecule segment
The adsorption capacities of various groups there is some difference, therefore boundary layer is also in the presence of certain with polymeric matrix in structure
Difference.Second stage is the cure stage of polymer.In polymeric matrix solidification process, boundary layer is concurrently cured to form fixation
Boundary layer.It is influenced by the first stage, cure stage can also have a certain difference, therefore two stage collective effects determine
The structure of boundary layer.
According to the forming process at interface it is found that composite material forms a transition region with multi-layer structure in interface
Domain, the region can usually be rendered as change of gradient due to chemical constituent difference, strand arrangement, hot property difference etc..Interface
The moulding process of the performance of layer and polymeric matrix, the property of second phase particles, the property of interfacial compatibilizer and composite material
Etc. closely related.Interface is the tie being connected between second phase particles and resin matrix, to the physics, chemistry and power of composite material
Learning performance has vital influence.In the composite, there is good interface cohesion between second phase particles and matrix
When, mechanical property is not simply to sum it up, it is possible to produce the synergy of 1+1 > 2, generate synergy the reason of may
It is performance or structure etc..
Core-shell copolymerized object
There are many structure type of core-shell particles, can be single layer and are also possible to multilayer, stratum nucleare part can be soft core (rubber
State), or stone (glassy state), but shell sections have to have certain compatibility with body portion, and it otherwise can be to base
The whole physical and chemical performance of body impacts.Practical study shows additive amount, particle diameter distribution and the matrix of core-shell copolymerized object
Compatibility, glass transition temperature, the content of stratum nucleare, the degree of cross linking, the toughness of matrix can all be caused with the adhesiveness of matrix
It influences.The selection of suitable core-shell copolymerized object needs to pay creative labor.
It is that nucleocapsid structure is modified that core-shell copolymerized object, which is used as plasticized modifier and the maximum difference of other type modifying agent,
The size of the particle of agent has just been determined in the synthesis process, is carrying out that any change will not occur when processing is blended with matrix
Become.In this case, so that it may which the core-shell structure modifying agent for designing the optimum size with partial size in advance comes to polymer
It is modified, and does not have to consider influence of other various factors to its size.
In a preferred embodiment, the raw material for preparing of the core-shell copolymerized object is selected from acrylate and its derivative
Object, methacrylate and its derivative, butadiene and its derivative, Styrene and its derivatives, acrylonitrile and its derivative
At least one of.
In a preferred embodiment, the core-shell copolymerized object is selected from (methyl methacrylate-methacrylic acid
Butyl ester-styrene) core-shell copolymerized object, (methyl methacrylate-butyl methacrylate-butadiene) core-shell copolymerized object, methyl
Methylacrylate-butadiene-styrol copolymer, acrylonitrile-butadiene-styrene copolymer, polystyrene-polybutadiene-
Polystyrene block copolymer or polystyrene-polybutadiene-polymethylmethacrylablock block copolymer, siloxane-methyl
At least one of acrylic acid methyl copolymer, Plastoid B.
In a preferred embodiment, the core-shell copolymerized object is (methyl methacrylate-methacrylic acid fourth
Ester-styrene) core-shell copolymerized object and (methyl methacrylate-butyl methacrylate-butadiene) core-shell copolymerized object mixing
Object, wherein (methyl methacrylate-butyl methacrylate-styrene) core-shell copolymerized object and (methyl methacrylate-methyl
Butyl acrylate-butadiene) mass ratio of core-shell copolymerized object is 1.75~3.5:1.
In a preferred embodiment, the core-shell copolymerized object is (methyl methacrylate-methacrylic acid fourth
Ester-styrene) core-shell copolymerized object and (methyl methacrylate-butyl methacrylate-butadiene) core-shell copolymerized object mixing
Object, wherein (methyl methacrylate-butyl methacrylate-styrene) core-shell copolymerized object and (methyl methacrylate-methyl
Butyl acrylate-butadiene) mass ratio of core-shell copolymerized object is 2.5:1.
(methyl methacrylate-butyl methacrylate-styrene) core-shell copolymerized object of the invention is commercial product, tool
It is to body the product that the chemical trade mark in clock deep pool is M210.(methyl methacrylate-butyl methacrylate-butadiene) of the invention
Core-shell copolymerized object is commercial product, in particular the chemical trade mark in clock deep pool be M270 product.
In a preferred embodiment, the modified poly (methyl methacrylate) composition further includes 2~10 parts
Modified manometer silicon dioxide.
In a preferred embodiment, the mass ratio of the modified manometer silicon dioxide and core-shell type is
1:3~15.
In a preferred embodiment, the mass ratio of the modified manometer silicon dioxide and core-shell type is
1:7.
In a preferred embodiment, the preparation method of the modified manometer silicon dioxide includes at least following step
It is rapid:
A. the reaction kettle with mechanical stirring and nitrogen protection is heated to 100 DEG C of displacement oxygen, it is cooling to lead to nitrogen, successively plus
Enter hydroxy-ethyl acrylate, three (2- dimethylaminoethyl) amine and CuBr, wherein hydroxy-ethyl acrylate, three (2- dimethylaminoethyls)
The mass ratio of amine and CuBr are 100:0.5~2:0.5~1, after stirring 15~40min in the presence of nitrogen, are drawn with syringe injection
The molar ratio of hair agent 2- methyl chloropropionate, 2- methyl chloropropionate and hydroxy-ethyl acrylate is 0.4~1.2:100, is warming up to 100 DEG C
Stop reaction after reacting 4h under stiring, it is cooling.Tetrahydrofuran dissolution is added, crosses Al2O3After pillar removes catalyst, it will react
Solution is slowly dropped in dehydrated alcohol and precipitates, and stirs when being added dropwise.After filtering off clear liquid, constant weight is dried under vacuum to by 60 DEG C of product
Obtain product a.
B. the 250mL reaction kettle for having nitrogen atmosphere to protect is heated to 100 DEG C of displacement oxygen, after cooling, is protected in nitrogen atmosphere
Under sequentially add the cyclohexanone solution, (2- dimethylaminoethyl) amine and CuBr of 1,3-butadiene, wherein 1,3-butadiene, (2-
Dimethylaminoethyl) mass ratio of amine and CuBr is 100:0.5~2:0.5~1, the concentration of the cyclohexanone solution of 1,3-butadiene
For 10~15wt%, after stirring 15~40min, the product a synthesized above, the matter of product a and 1,3-butadiene are added thereto
Amount is warming up to 60 DEG C, continues to stop reaction after logical nitrogen reacts 2~4h under stiring than being 1~2:1.Cross Al2O3Pillar removes
After catalyst, reaction solution is slowly dropped in n-hexane and is precipitated, stirred when being added dropwise.After filtering off clear liquid, by 40 DEG C of product
It is dried under vacuum to constant weight and obtains product b.
C. the 250mL reaction kettle for having nitrogen protection is heated to 100 DEG C of displacement oxygen, after cooling, sequentially add dimethylbenzene,
Gamma-methyl allyl acyloxypropyl trimethoxysilane, (2- dimethylaminoethyl) amine and CuCl, wherein dimethylbenzene, γ-methyl-prop
The mass ratio of alkene monomethacryloxypropyl trimethoxy silane, (2- dimethylaminoethyl) amine and CuCl is 100:20~25:0.1~1:
0.1~0.5, after stirring 30min, product b, the matter of product b and gamma-methyl allyl acyloxypropyl trimethoxysilane is then added
Amount is warming up to 120 DEG C than being 20:3~7.Purification step ibid obtains product c after reaction.
D. nano silica is placed at calcined 3 hours at 300 DEG C after again at 400 DEG C calcine 2h be placed in drier
For use.Product c is configured to the tetrahydrofuran solution that mass concentration is 5~20%, nano silica is completely submerged in institute
In the tetrahydrofuran solution stated, wherein the mass ratio of nano silica and product c are 4~6:1, are sealed, in earthquake shaking table
Product is taken out after concussion 40min, after natural drying, is dried half an hour in 90 DEG C of baking ovens, then heats one section in 120 DEG C of baking ovens
Then time elutes 48h in Soxhlet extractor tetrahydrofuran solution, is dried to obtain the modified manometer silicon dioxide.
In a preferred embodiment, the partial size of the nano silica is 0~100nm.
In a preferred embodiment, the partial size of the nano silica is 50~80nm.
It in a preferred embodiment, by weight, further include the auxiliary agent of 0.1~5 parts by weight.
In a preferred embodiment, the auxiliary agent is selected from antioxidant, light stabilizer, ultraviolet absorber, lubrication
At least one of agent, colorant.
In a preferred embodiment, the antioxidant is selected from least one of phosphite ester, hindered phenol.
In a preferred embodiment, the light stabilizer is stablized 770, light selected from light and is stablized in 622 at least
It is a kind of.
In a preferred embodiment, the ultraviolet absorbing agent is in UV-234, UV-328, UV-320
It is at least one.
In a preferred embodiment, the lubricant is selected from polyethylene wax, oxidized polyethylene wax, pentaerythrite
Stearate, long chain fatty acids polyfunctional group ester, zinc stearate, fatty acid amide, calcium stearate, polyethylene wax, ethylene are double hard
At least one of resin acid amide.
In a preferred embodiment, the preparation method of the modified poly (methyl methacrylate) composition, until
Less the following steps are included:
By weight, high speed mixer is added the raw material into be mixed, temperature be 10~40 DEG C, revolving speed be 200~
It is transferred into circulating baking oven after 500rpm, 90~180s, handles 1~3h at 80 DEG C, is then put into twin-screw and squeezed
Out in machine, extruding pelletization under conditions of 190~220 DEG C, by obtained particle by hoisting type homogenizing bin at 70~90 DEG C
20~40min of lower homogenizing obtains the modified poly (methyl methacrylate) composition.
In a preferred embodiment, the modified poly (methyl methacrylate) composition is in manufacture optical device
In purposes, the optical device is preferably board of glasses.
The present invention is surface-treated nano silica by the copolymer with flexible blocks, can be in nano-silica
Interface flexible layer is introduced in SiClx and composite material of polymethyl methacrylate, the presence of interface flexible layer can slow down stress collection
In, uniformly transfer stress, can effectively relax thermal stress, thus increase substantially absorb impact energy ability, to improve
The toughness of polymethyl methacrylate.In addition the present invention is modified by two kinds of nucleocapsid copolymers with modified manometer silicon dioxide poly-
Methyl methacrylate is improved the toughness of material, and remains the spies such as the original high grade of transparency of PMMA, high gloss
Property.The plate of modified PMMA production can satisfy the manufacture craft and processing request of plate glasses, and solving PMMA cannot apply
In eye glass frame production the problem of.And compared to the plate and plate glasses of " acetic acid " production, size is more stable.Greatly improve
The yield rate of product, and reduce production cost and after cost.
Essence in order to better understand the present invention, it is following to give embodiments of the present invention, it is merely to illustrate this hair
Bright how to implement, not the limitation present invention can only be implemented by following scheme, on the basis of understanding technical solution of the present invention,
Change, replacement, structural modification carried out to the present invention etc. still belongs to the scope of protection of the present invention, and protection scope of the present invention is contained
It is placed on its claim and its equivalents.Unless stated otherwise, reagent, method involved in embodiment are that this field is normal
Reagent and method.
Embodiment 1:
Embodiment 1 provides a kind of modified poly (methyl methacrylate) composition, by weight, includes at least with the following group
Point: 40 parts of polymethyl methacrylate, 10 parts of core-shell copolymerized object.
The core-shell copolymerized object be (methyl methacrylate-butyl methacrylate-styrene) core-shell copolymerized object and
The mixture of (methyl methacrylate-butyl methacrylate-butadiene) core-shell copolymerized object, wherein (methyl methacrylate-
Butyl methacrylate-styrene) core-shell copolymerized object and (methyl methacrylate-butyl methacrylate-butadiene) nucleocapsid
The mass ratio of copolymer is 1.75:1.
It further include the auxiliary agent of 0.8 parts by weight, the auxiliary agent packet in the modified poly (methyl methacrylate) composition
The lubricant stearic acid zinc of the antioxidant phosphite ester of 0.2 parts by weight, the hindered phenol of 0.2 parts by weight and 0.4 parts by weight is included,
Phosphorous acid ester is the product that the Japanese Ai Dika company trade mark is PEP-36, and the hindered phenol is Ai Dika company of the Japan trade mark
For the product of AO-60.
The preparation method of the modified poly (methyl methacrylate) composition, at least includes the following steps:
By weight, it adds the raw material into high speed mixer to be mixed, temperature is 40 DEG C, revolving speed 300rpm, 120s
After be transferred into circulating baking oven, 2h is handled at 80 DEG C, is then put into double screw extruder, at 195~215 DEG C
Under conditions of extruding pelletization, obtained particle is homogenized 30min at 70~80 DEG C by hoisting type homogenizing bin, is obtained described
Modified poly (methyl methacrylate) composition.
Embodiment 2:
Embodiment 2 provides a kind of modified poly (methyl methacrylate) composition, by weight, includes at least with the following group
Point: 80 parts of polymethyl methacrylate, 65 parts of core-shell copolymerized object.
The core-shell copolymerized object be (methyl methacrylate-butyl methacrylate-styrene) core-shell copolymerized object and
The mixture of (methyl methacrylate-butyl methacrylate-butadiene) core-shell copolymerized object, wherein (methyl methacrylate-
Butyl methacrylate-styrene) core-shell copolymerized object and (methyl methacrylate-butyl methacrylate-butadiene) nucleocapsid
The mass ratio of copolymer is 3.5:1.
It further include the auxiliary agent of 0.8 parts by weight, the auxiliary agent packet in the modified poly (methyl methacrylate) composition
The lubricant stearic acid zinc of the antioxidant phosphite ester of 0.2 parts by weight, the hindered phenol of 0.2 parts by weight and 0.4 parts by weight is included,
Phosphorous acid ester is the product that the Japanese Ai Dika company trade mark is PEP-36, and the hindered phenol is Ai Dika company of the Japan trade mark
For the product of AO-60.
The preparation method is the same as that of Example 1 for the modified poly (methyl methacrylate) composition.
Embodiment 3:
Embodiment 3 provides the modified poly (methyl methacrylate) composition, by weight, includes at least following
Component: 50 parts of polymethyl methacrylate, 60 parts of core-shell copolymerized object.
The core-shell copolymerized object be (methyl methacrylate-butyl methacrylate-styrene) core-shell copolymerized object and
The mixture of (methyl methacrylate-butyl methacrylate-butadiene) core-shell copolymerized object, wherein (methyl methacrylate-
Butyl methacrylate-styrene) core-shell copolymerized object and (methyl methacrylate-butyl methacrylate-butadiene) nucleocapsid
The mass ratio of copolymer is 2.5:1.
It further include the auxiliary agent of 0.8 parts by weight, the auxiliary agent packet in the modified poly (methyl methacrylate) composition
The lubricant stearic acid zinc of the antioxidant phosphite ester of 0.2 parts by weight, the hindered phenol of 0.2 parts by weight and 0.4 parts by weight is included,
Phosphorous acid ester is the product that the Japanese Ai Dika company trade mark is PEP-36, and the hindered phenol is Ai Dika company of the Japan trade mark
For the product of AO-60.
The preparation method is the same as that of Example 1 for the modified poly (methyl methacrylate) composition.
Embodiment 4:
Embodiment 4 provides the modified poly (methyl methacrylate) composition, by weight, includes at least following
Component: 60 parts of polymethyl methacrylate, 49 parts of core-shell copolymerized object.
The core-shell copolymerized object be (methyl methacrylate-butyl methacrylate-styrene) core-shell copolymerized object and
The mixture of (methyl methacrylate-butyl methacrylate-butadiene) core-shell copolymerized object, wherein (methyl methacrylate-
Butyl methacrylate-styrene) core-shell copolymerized object and (methyl methacrylate-butyl methacrylate-butadiene) nucleocapsid
The mass ratio of copolymer is 2.5:1.
It further include the auxiliary agent of 0.8 parts by weight, the auxiliary agent packet in the modified poly (methyl methacrylate) composition
The lubricant stearic acid zinc of the antioxidant phosphite ester of 0.2 parts by weight, the hindered phenol of 0.2 parts by weight and 0.4 parts by weight is included,
Phosphorous acid ester is the product that the Japanese Ai Dika company trade mark is PEP-36, and the hindered phenol is Ai Dika company of the Japan trade mark
For the product of AO-60.
The preparation method is the same as that of Example 1 for the modified poly (methyl methacrylate) composition.
Embodiment 5:
Embodiment 5 provides a kind of modified poly (methyl methacrylate) composition, by weight, includes at least with the following group
Point: 60 parts of polymethyl methacrylate, 49 parts of core-shell copolymerized object.
The core-shell copolymerized object be (methyl methacrylate-butyl methacrylate-styrene) core-shell copolymerized object and
The mixture of (methyl methacrylate-butyl methacrylate-butadiene) core-shell copolymerized object, wherein (methyl methacrylate-
Butyl methacrylate-styrene) core-shell copolymerized object and (methyl methacrylate-butyl methacrylate-butadiene) nucleocapsid
The mass ratio of copolymer is 2.5:1.
The modified poly (methyl methacrylate) composition further includes 2 parts of modified manometer silicon dioxide.
The preparation method of the modified manometer silicon dioxide at least includes the following steps:
A. the reaction kettle with mechanical stirring and nitrogen protection is heated to 100 DEG C of displacement oxygen, it is cooling to lead to nitrogen, successively plus
Enter hydroxy-ethyl acrylate, three (2- dimethylaminoethyl) amine and CuBr, wherein hydroxy-ethyl acrylate, three (2- dimethylaminoethyls)
The mass ratio of amine and CuBr are 100:1:0.5, after stirring 30min in the presence of nitrogen, inject initiator 2- chloropropionic acid with syringe
The molar ratio of methyl esters, 2- methyl chloropropionate and hydroxy-ethyl acrylate be 0.6:100, be warming up to 100 DEG C under stiring react 4h after
Stop reaction, it is cooling.Tetrahydrofuran dissolution is added, crosses Al2O3After pillar removes catalyst, reaction solution is slowly dropped to nothing
It precipitates in water-ethanol, is stirred when being added dropwise.After filtering off clear liquid, constant weight is dried under vacuum to by 60 DEG C of product and obtains product a.
B. the 250mL reaction kettle for having nitrogen atmosphere to protect is heated to 100 DEG C of displacement oxygen, after cooling, is protected in nitrogen atmosphere
Under sequentially add the cyclohexanone solution, (2- dimethylaminoethyl) amine and CuBr of 1,3-butadiene, wherein 1,3-butadiene, (2-
Dimethylaminoethyl) mass ratio of amine and CuBr is 100:1.2:0.6, the concentration of the cyclohexanone solution of 1,3-butadiene is
15wt%, after stirring 30min, the mass ratio of the product a that addition synthesizes above thereto, product a and 1,3-butadiene is 1.5:
1,60 DEG C are warming up to, stops reaction after continuing logical nitrogen reaction 4h under stiring.Cross Al2O3After pillar removes catalyst, it will react
Solution is slowly dropped in n-hexane and precipitates, and stirs when being added dropwise.After filtering off clear liquid, constant weight is dried under vacuum to by 40 DEG C of product and is obtained
To product b.
C. the 250mL reaction kettle for having nitrogen protection is heated to 100 DEG C of displacement oxygen, after cooling, sequentially add dimethylbenzene,
Gamma-methyl allyl acyloxypropyl trimethoxysilane, (2- dimethylaminoethyl) amine and CuCl, wherein dimethylbenzene, γ-methyl-prop
The mass ratio of alkene monomethacryloxypropyl trimethoxy silane, (2- dimethylaminoethyl) amine and CuCl is 100:25:0.4:0.2, stirring
After 30min, then the mass ratio of addition product b, product b and gamma-methyl allyl acyloxypropyl trimethoxysilane is 20:6, is risen
Temperature is to 120 DEG C.Purification step ibid obtains product c after reaction.
D. nano silica is placed at calcined 3 hours at 300 DEG C after again at 400 DEG C calcine 2h be placed in drier
For use.Product c is configured to the tetrahydrofuran solution that mass concentration is 10%, nano silica is completely submerged in described
In tetrahydrofuran solution, wherein the mass ratio of nano silica and product c are 5:1, are sealed, and are shaken in earthquake shaking table
Product is taken out after 40min, after natural drying, is dried half an hour in 90 DEG C of baking ovens, then in 120 DEG C of baking ovens at one section of heating
Between, 48h then is eluted in Soxhlet extractor tetrahydrofuran solution, is dried to obtain the modified manometer silicon dioxide.
The size of the nano silica is 200 mesh, is purchased from Shijiazhuang gold and nano chemical Co., Ltd.
The preparation method of the modified manometer silicon dioxide is the same as embodiment 4.
The size of the nano silica is 200 mesh, is purchased from Shijiazhuang gold and nano chemical Co., Ltd.
It further include the auxiliary agent of 0.8 parts by weight, the auxiliary agent packet in the modified poly (methyl methacrylate) composition
The lubricant stearic acid zinc of the antioxidant phosphite ester of 0.2 parts by weight, the hindered phenol of 0.2 parts by weight and 0.4 parts by weight is included,
Phosphorous acid ester is the product that the Japanese Ai Dika company trade mark is PEP-36, and the hindered phenol is Ai Dika company of the Japan trade mark
For the product of AO-60.
The preparation method is the same as that of Example 1 for the modified poly (methyl methacrylate) composition.
Embodiment 6:
Embodiment 6 provides a kind of modified poly (methyl methacrylate) composition, by weight, includes at least with the following group
Point: 60 parts of polymethyl methacrylate, 49 parts of core-shell copolymerized object.
The core-shell copolymerized object be (methyl methacrylate-butyl methacrylate-styrene) core-shell copolymerized object and
The mixture of (methyl methacrylate-butyl methacrylate-butadiene) core-shell copolymerized object, wherein (methyl methacrylate-
Butyl methacrylate-styrene) core-shell copolymerized object and (methyl methacrylate-butyl methacrylate-butadiene) nucleocapsid
The mass ratio of copolymer is 2.5:1.
The modified poly (methyl methacrylate) composition further includes 7 parts of modified manometer silicon dioxide.
The preparation method of the modified manometer silicon dioxide is the same as embodiment 5.
The size of the nano silica is 200 mesh, is purchased from Shijiazhuang gold and nano chemical Co., Ltd.
It further include the auxiliary agent of 0.8 parts by weight, the auxiliary agent packet in the modified poly (methyl methacrylate) composition
The lubricant stearic acid zinc of the antioxidant phosphite ester of 0.2 parts by weight, the hindered phenol of 0.2 parts by weight and 0.4 parts by weight is included,
Phosphorous acid ester is the product that the Japanese Ai Dika company trade mark is PEP-36, and the hindered phenol is Ai Dika company of the Japan trade mark
For the product of AO-60.
The preparation method is the same as that of Example 1 for the modified poly (methyl methacrylate) composition.
Comparative example 1:
The specific embodiment of comparative example 1 with embodiment 6, the difference is that, do not include core-shell copolymerized object and modification receive
Rice silica.
Comparative example 2:
The specific embodiment of comparative example 2 with embodiment 6, the difference is that, do not include (methyl methacrylate-first
Base butyl acrylate-styrene) core-shell copolymerized object.
Comparative example 3:
The specific embodiment of comparative example 3 with embodiment 6, the difference is that, do not include (methyl methacrylate-first
Base butyl acrylate-butadiene) core-shell copolymerized object.
Comparative example 4:
The specific embodiment of comparative example 4 with embodiment 6, the difference is that, (the methyl methacrylate-first
Base butyl acrylate-styrene) core-shell copolymerized object and (methyl methacrylate-butyl methacrylate-butadiene) nucleocapsid it is total
The mass ratio of polymers is 1:1.
Comparative example 5:
The specific embodiment of comparative example 5 with embodiment 6, the difference is that, improved silica such as is changed at the matter
The silica of amount.
Comparative example 6:
The specific embodiment of comparative example 6 with embodiment 6, the difference is that, the partial size of the silica is
1000 mesh are purchased from Shijiazhuang gold and nano chemical Co., Ltd.
Performance evaluation:
1. physical property measurement
A. Charpy Impact/notch impact strength is tested according to ISO-179/1eU, ISO-179/1eA；
B. Chalpy impact/notch impact strength is tested according to ISO-180, ISO-180/1A；
C. tensile break strength/elongation at break is tested according to ISO-527；
Test data is as shown in table 1.
1 physical property measurement of table
Note: subscript 1 shows that test condition is 50mm/min in field；Subscript 2 shows that test condition is 5mm/min.
2. glasses processing technology is tested
The test of 2 glasses processing technology of table
| Lathe " milling circle " | Lathe " finishing impression " | Hot pressing " central sill " | It heats " face is curved " | It heats " curved spleen " | |
| Embodiment 1 | Normal process | Normal process | Normal process | Normal process | Normal process |
| Embodiment 2 | Normal process | Normal process | Normal process | Normal process | Normal process |
| Embodiment 3 | Normal process | Normal process | Normal process | Normal process | Normal process |
| Embodiment 4 | Normal process | Normal process | Normal process | Normal process | Normal process |
| Embodiment 5 | Normal process | Normal process | Normal process | Normal process | Normal process |
| Embodiment 6 | Normal process | Normal process | Normal process | Normal process | Normal process |
| Comparative example 1 | Fracture | Fracture | Fracture | Fracture | Fracture |
| Comparative example 2 | Fracture | Fracture | Normal process | Normal process | Normal process |
| Comparative example 3 | Fracture | Fracture | Normal process | Normal process | Normal process |
| Comparative example 4 | Fracture | Fracture | Normal process | Normal process | Normal process |
| Comparative example 5 | Normal process | Normal process | Fracture | Fracture | Fracture |
| Comparative example 6 | Normal process | Normal process | Fracture | Fracture | Fracture |
3. dimensional stability
By taking the modified poly (methyl methacrylate) composition that embodiment 4 and comparative example 1 obtain as an example, according to ISO-16570/
Method described in 4, tests its dimensional stability test after high/low temperature loop test, and test result is as shown in table 3.In experiment
Circulating temperature and relative humidity variations curve are as shown in Figure 1.
The test of 3 dimensional stability of table
From table 1~3 it is found that modified poly (methyl methacrylate) composition of the invention is lacked in Charpy Impact, simply supported beam
Mouthful impact, Chalpy impact, Izod notched impact, tensile break strength, elongation at break test in show it is excellent
Performance has splendid toughness and hardness, while by the way that modified material is reasonably selected and compounded, the PMMA material made
Retain the characteristics such as its original high grade of transparency, high gloss.The plate of modified PMMA production can satisfy the production of plate glasses
Technique and processing request solve the problems, such as that PMMA may not apply to eye glass frame production.And compared to the plate of " acetic acid " production
With plate glasses, size is more stable.The yield rate of product greatly is improved, and reduces production cost and after cost.
The above described is only a preferred embodiment of the present invention, being not that the invention has other forms of limitations, appoint
What those skilled in the art changed or be modified as possibly also with the technology contents of above-mentioned enlightenment equivalent variations etc.
Imitate embodiment.But everything is without departing from technical solution of the present invention content, according to the technical essence of the invention to above embodiments institute
The simple modification made, equivalent variations and remodeling, still fall within the protection scope of technical solution of the present invention.
Claims (10)
1. a kind of modified poly (methyl methacrylate) composition, which is characterized in that by weight, include at least following components:
40~80 parts of polymethyl methacrylate, 10~65 parts of core-shell copolymerized object.
2. modified poly (methyl methacrylate) composition as described in claim 1, which is characterized in that by weight, at least
Including following components: 50~65 parts of polymethyl methacrylate, 30~60 parts of core-shell copolymerized object.
3. modified poly (methyl methacrylate) composition as described in claim 1, which is characterized in that the core-shell copolymerized object
Prepare raw material be selected from acrylate and its derivative, methacrylate and its derivative, butadiene and its derivative, benzene second
At least one of alkene and its derivative, acrylonitrile and its derivative.
4. modified poly (methyl methacrylate) composition as claimed in claim 3, which is characterized in that the core-shell copolymerized object
Selected from (methyl methacrylate-butyl methacrylate-styrene) core-shell copolymerized object, (methyl methacrylate-metering system
At least one of acid butyl ester-butadiene) core-shell copolymerized object.
5. modified poly (methyl methacrylate) composition as claimed in claim 4, which is characterized in that the core-shell copolymerized object
For (methyl methacrylate-butyl methacrylate-styrene) core-shell copolymerized object and (methyl methacrylate-metering system
Acid butyl ester-butadiene) core-shell copolymerized object mixture, wherein (methyl methacrylate-butyl methacrylate-styrene) core
The mass ratio of shell copolymer and (methyl methacrylate-butyl methacrylate-butadiene) core-shell copolymerized object is 1.75~
3.5:1.
6. modified poly (methyl methacrylate) composition as described in claim 1, which is characterized in that further include 2~10 parts
Modified manometer silicon dioxide.
7. modified poly (methyl methacrylate) composition as described in claim 1, which is characterized in that by weight, also wrap
Include the auxiliary agent of 0.1~5 parts by weight.
8. modified poly (methyl methacrylate) composition as claimed in claim 7, which is characterized in that the auxiliary agent is selected from anti-
At least one of oxygen agent, light stabilizer, ultraviolet absorber, lubricant, colorant.
9. the preparation method of modified poly (methyl methacrylate) composition as described in any one of claims 1 to 8, feature exist
In at least including the following steps:
By weight, high speed mixer being added the raw material into be mixed, temperature is 10~40 DEG C, and revolving speed is 200~500rpm,
It is transferred into circulating baking oven after 90~180s, handles 1~3h at 80 DEG C, is then put into double screw extruder,
Obtained particle is homogenized 20 at 70~90 DEG C by hoisting type homogenizing bin by extruding pelletization under conditions of 190~220 DEG C
~40min obtains the modified poly (methyl methacrylate) composition.
10. modified poly (methyl methacrylate) composition as described in any one of claims 1 to 8 is in manufacture optical device
Purposes, the optical device are preferably board of glasses.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810749743.7A CN109054270B (en) | 2018-07-10 | 2018-07-10 | Modified polymethyl methacrylate composition and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810749743.7A CN109054270B (en) | 2018-07-10 | 2018-07-10 | Modified polymethyl methacrylate composition and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109054270A true CN109054270A (en) | 2018-12-21 |
| CN109054270B CN109054270B (en) | 2021-06-15 |
Family
ID=64819411
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810749743.7A Active CN109054270B (en) | 2018-07-10 | 2018-07-10 | Modified polymethyl methacrylate composition and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109054270B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110441921A (en) * | 2019-06-27 | 2019-11-12 | 创彰科技（深圳）有限公司 | Transparent glasses frame based on modified material |
| CN110684310A (en) * | 2019-11-06 | 2020-01-14 | 中广核俊尔（上海）新材料有限公司 | High-rigidity high-toughness modified PMMA material and preparation method thereof |
| CN114230998A (en) * | 2021-09-17 | 2022-03-25 | 无锡德塑新材料科技有限公司 | PC/PS/PMMA ternary alloy material and preparation method thereof |
| CN114752169A (en) * | 2022-03-22 | 2022-07-15 | 苏州新华美塑料有限公司 | High-impact transparent PMMA composite material filled with optical rod waste modified powder and preparation method thereof |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101575464A (en) * | 2009-05-25 | 2009-11-11 | 苏州大学 | Method for preparing PMMA impact resistant material applied to laser marking |
| CN103073829A (en) * | 2012-12-31 | 2013-05-01 | 青岛润兴塑料新材料有限公司 | Spraying-free metallic PMMA (polymethyl methacrylate) modified material and preparation method thereof |
| CN103387732A (en) * | 2013-08-01 | 2013-11-13 | 太仓市晨洲塑业有限公司 | Formula of modified polymethyl methacrylate |
| CN104456352A (en) * | 2014-11-13 | 2015-03-25 | 宁波市鄞州雅佳达车业有限公司 | Steering lamp |
| CN104456354A (en) * | 2014-11-13 | 2015-03-25 | 宁波雅佳达电器有限公司 | Motorcycle headlamp |
| CN105885320A (en) * | 2016-06-13 | 2016-08-24 | 上海金山锦湖日丽塑料有限公司 | PMMA resin with ultrahigh toughness |
| CN107118480A (en) * | 2017-05-05 | 2017-09-01 | 安徽科聚新材料有限公司 | PMMA/ASA composites and preparation method thereof |
| KR101849197B1 (en) * | 2016-12-30 | 2018-04-17 | 주식회사 효성 | Methods for preparing acryl film |
| CN109810439A (en) * | 2017-11-22 | 2019-05-28 | 万华化学集团股份有限公司 | Plexiglass composition and its preparation method and application with aesthetic look and improvement heat resistance |
-
2018
- 2018-07-10 CN CN201810749743.7A patent/CN109054270B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101575464A (en) * | 2009-05-25 | 2009-11-11 | 苏州大学 | Method for preparing PMMA impact resistant material applied to laser marking |
| CN103073829A (en) * | 2012-12-31 | 2013-05-01 | 青岛润兴塑料新材料有限公司 | Spraying-free metallic PMMA (polymethyl methacrylate) modified material and preparation method thereof |
| CN103387732A (en) * | 2013-08-01 | 2013-11-13 | 太仓市晨洲塑业有限公司 | Formula of modified polymethyl methacrylate |
| CN104456352A (en) * | 2014-11-13 | 2015-03-25 | 宁波市鄞州雅佳达车业有限公司 | Steering lamp |
| CN104456354A (en) * | 2014-11-13 | 2015-03-25 | 宁波雅佳达电器有限公司 | Motorcycle headlamp |
| CN105885320A (en) * | 2016-06-13 | 2016-08-24 | 上海金山锦湖日丽塑料有限公司 | PMMA resin with ultrahigh toughness |
| KR101849197B1 (en) * | 2016-12-30 | 2018-04-17 | 주식회사 효성 | Methods for preparing acryl film |
| CN107118480A (en) * | 2017-05-05 | 2017-09-01 | 安徽科聚新材料有限公司 | PMMA/ASA composites and preparation method thereof |
| CN109810439A (en) * | 2017-11-22 | 2019-05-28 | 万华化学集团股份有限公司 | Plexiglass composition and its preparation method and application with aesthetic look and improvement heat resistance |
Non-Patent Citations (1)
| Title |
|---|
| 丁进: "ABS/PMMA共混体系增韧改性研究", 《中国博士学位论文全文数据库工程科技Ⅰ辑》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110441921A (en) * | 2019-06-27 | 2019-11-12 | 创彰科技（深圳）有限公司 | Transparent glasses frame based on modified material |
| CN110684310A (en) * | 2019-11-06 | 2020-01-14 | 中广核俊尔（上海）新材料有限公司 | High-rigidity high-toughness modified PMMA material and preparation method thereof |
| CN114230998A (en) * | 2021-09-17 | 2022-03-25 | 无锡德塑新材料科技有限公司 | PC/PS/PMMA ternary alloy material and preparation method thereof |
| CN114752169A (en) * | 2022-03-22 | 2022-07-15 | 苏州新华美塑料有限公司 | High-impact transparent PMMA composite material filled with optical rod waste modified powder and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109054270B (en) | 2021-06-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109054270A (en) | A kind of modified poly (methyl methacrylate) composition and preparation method thereof, application | |
| US4528351A (en) | Plastic lens | |
| JP2012518052A (en) | Acrylic resin composition and optical film containing the same | |
| WO1996006370A1 (en) | Non-birefringent optical resin material and method of manufacturing the same, and member of liquid crystal elements using optical resin material | |
| JP2011519389A (en) | Resin composition and optical film formed using the same | |
| CN1643435A (en) | Polymerization process and materials for biomedical applications | |
| TW200946583A (en) | Light-scattering compositions | |
| CN107501829A (en) | A kind of automobile-used resistance to thermal level exempts to spray PMMA/ASA alloys | |
| CN110437599A (en) | A kind of PC/PMMA alloy material and preparation method thereof | |
| Lipatov et al. | Gradient interpenetrating polymer networks | |
| JP7124050B2 (en) | Resin composition and dope for film production by solution casting method | |
| CN111978459A (en) | PMMA/glass fiber composite material and preparation method and application thereof | |
| JPH10501898A (en) | Non-birefringent optical adhesive and thin film | |
| JPS5986615A (en) | Polymerizable composition | |
| Zhang et al. | Acrylonitrile‐Styrene‐Acrylate Particles with Different Microstructure for Improving the Toughness of Poly (styrene‐co‐acrylonitrile) Resin | |
| WO2022131365A1 (en) | Graft copolymer and resin film | |
| JP2007514795A (en) | Method for producing an article from a thermosetting resin | |
| JPH0249009A (en) | Monomer composition | |
| JPS60197711A (en) | High-refractive index resin composition | |
| CN103608397B (en) | Resin composition and optical compensation film formed by using same | |
| KR102187883B1 (en) | Coating composition of multi function epoxy and arcyl series and manufacturing method thereof | |
| KR101497180B1 (en) | Acryl copolymer having excellent strength, resin composition comprising the same, opticla film and ips mode liquid crystal display comprising thereof | |
| CN107513245A (en) | A kind of modified starch toughness reinforcing composite material of polymethyl methacrylate and preparation method | |
| CN115707735B (en) | High-hardness transparent polycarbonate material and preparation method and application thereof | |
| US4212697A (en) | Process for producing glass fiber-reinforced resin molded sheets |
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 |