CN109456440A - A kind of modified acroleic acid ester material and preparation method thereof - Google Patents
A kind of modified acroleic acid ester material and preparation method thereof Download PDFInfo
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- CN109456440A CN109456440A CN201811128603.4A CN201811128603A CN109456440A CN 109456440 A CN109456440 A CN 109456440A CN 201811128603 A CN201811128603 A CN 201811128603A CN 109456440 A CN109456440 A CN 109456440A
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- acid ester
- acroleic acid
- modified acroleic
- weight
- ester material
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- 239000000463 material Substances 0.000 title claims abstract description 139
- -1 modified acroleic acid ester Chemical class 0.000 title claims abstract description 114
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 104
- 239000002994 raw material Substances 0.000 claims abstract description 64
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 54
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000000178 monomer Substances 0.000 claims description 99
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 90
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 70
- 239000008367 deionised water Substances 0.000 claims description 69
- 229910021641 deionized water Inorganic materials 0.000 claims description 69
- 239000003995 emulsifying agent Substances 0.000 claims description 59
- 239000003999 initiator Substances 0.000 claims description 57
- 238000006243 chemical reaction Methods 0.000 claims description 51
- 239000000839 emulsion Substances 0.000 claims description 48
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 30
- 238000007334 copolymerization reaction Methods 0.000 claims description 27
- 230000033228 biological regulation Effects 0.000 claims description 15
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 15
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 15
- 238000010792 warming Methods 0.000 claims description 15
- 239000006210 lotion Substances 0.000 claims description 12
- 230000000694 effects Effects 0.000 claims description 8
- 239000012467 final product Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 230000003287 optical effect Effects 0.000 claims description 2
- 230000032683 aging Effects 0.000 abstract description 10
- 238000012360 testing method Methods 0.000 abstract description 9
- 230000035939 shock Effects 0.000 abstract description 8
- 230000000052 comparative effect Effects 0.000 description 21
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 21
- 229920000642 polymer Polymers 0.000 description 20
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 13
- 239000004926 polymethyl methacrylate Substances 0.000 description 13
- 150000002191 fatty alcohols Chemical class 0.000 description 12
- ONJQDTZCDSESIW-UHFFFAOYSA-N polidocanol Chemical compound CCCCCCCCCCCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO ONJQDTZCDSESIW-UHFFFAOYSA-N 0.000 description 12
- 229940051841 polyoxyethylene ether Drugs 0.000 description 12
- 229920000056 polyoxyethylene ether Polymers 0.000 description 12
- 238000013329 compounding Methods 0.000 description 11
- 238000001035 drying Methods 0.000 description 11
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical group [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 11
- 229910052939 potassium sulfate Inorganic materials 0.000 description 11
- 235000011151 potassium sulphates Nutrition 0.000 description 11
- 238000005406 washing Methods 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 10
- 238000007599 discharging Methods 0.000 description 10
- 239000006071 cream Substances 0.000 description 8
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 description 7
- 238000012986 modification Methods 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 150000003983 crown ethers Chemical class 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 150000004702 methyl esters Chemical class 0.000 description 3
- IIVTYEDFYGVHMR-UHFFFAOYSA-N n-ethoxyprop-2-enamide Chemical compound CCONC(=O)C=C IIVTYEDFYGVHMR-UHFFFAOYSA-N 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 235000019394 potassium persulphate Nutrition 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- YBXYCBGDIALKAK-UHFFFAOYSA-N 2-chloroprop-2-enamide Chemical compound NC(=O)C(Cl)=C YBXYCBGDIALKAK-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- UHTVKSHZHQJMBB-UHFFFAOYSA-N CCCCC=C(C)C(NC(C)C)=O Chemical compound CCCCC=C(C)C(NC(C)C)=O UHTVKSHZHQJMBB-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical class C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000003679 aging effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- SYWDWCWQXBUCOP-UHFFFAOYSA-N benzene;ethene Chemical group C=C.C1=CC=CC=C1 SYWDWCWQXBUCOP-UHFFFAOYSA-N 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- HXJGFDIZSMWOGY-UHFFFAOYSA-N n-(2-azaniumylethyl)prop-2-enimidate Chemical compound NCCNC(=O)C=C HXJGFDIZSMWOGY-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N n-hexanoic acid Natural products CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007634 remodeling Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Graft Or Block Polymers (AREA)
Abstract
The present invention relates to polymeric material field, a kind of modified acroleic acid ester material and preparation method thereof.The raw material for preparing of the modified acroleic acid ester material includes methyl methacrylate, butyl acrylate, butadiene, styrene.Modified acroleic acid ester material provided by the invention shows excellent performance in Charpy Impact, simply supported beam notch shock, Chalpy impact, Izod notched impact, tensile break strength, elongation at break test, with splendid toughness and hardness, it is reasonably selected and is configured by the raw material for preparing to modified material simultaneously, the modified acroleic acid ester material made retains the characteristics such as its original high grade of transparency and low haze.In addition, the modified acroleic acid ester material has very strong ageing-resistant performance, it can satisfy product and non-aging requirement be used for a long time, improve the service life and running efficiency of instrument.
Description
Technical field
The present invention relates to polymeric material field, a kind of modified acroleic acid ester material and preparation method thereof.
Background technique
Polymethyl methacrylate (PMMA is commonly called as organic glass, acryl or acrylic) has crystal general transparent
Degree, light transmittance have good color development effect up to 92% or more, with dyestuff coloring.In addition, PMMA has splendid weatherability, higher
Surface hardness and lustrous surface and preferable high-temperature behavior.PMMA in aviation, automobile, electronics, medical treatment, chemical industry, building materials, defend
The industries such as bath and Advertisement label are widely used.
But ordinary PMMA resin is since extensibility is lower, and it is easy to crack, frangible, limit its further application.In the market
The PMMA of high-impact is the TF0956 of the first woolens of Samsung, but the material poor fluidity, not easily molded, is difficult to large thin-wall system
The molding of part.
Therefore preparation has the characteristics that the PMMA of high transparency, high-impact, good fluidity, heat resistance and good stability of the dimension
Material is the hot spot of each engineering plastic modification producer and the research of each scientific research institution.However, such as improving being modified in a certain respect
During heat resistance modified, dimensional stability modification etc., rigid unitary or highly polar monomer can be generally introduced in PMMA polymer
Be copolymerized, but often resulting PMMA polymer intensity, thermal stability or dimensional stability obtain improve while, resist
The performances such as impact strength, transparency reduce instead, cannot prepare the PMMA material for the good combination property having had both, so that influencing should
The application of material.
Summary of the invention
In order to solve the above-mentioned technical problem, the first aspect of the present invention provides a kind of modified acroleic acid ester material, special
Sign is that the raw material for preparing of the modified acroleic acid ester material includes methyl methacrylate, butyl acrylate, butadiene, benzene
Ethylene.
As a kind of perferred technical scheme, the molal weight of the methyl methacrylate is greater than or equal to, the fourth
The sum of the molal weight of diene and the butyl acrylate.
As a kind of perferred technical scheme, the modified acroleic acid ester material prepares raw material, in parts by weight, including
Methyl methacrylate 35~50, butyl acrylate 15~20, butadiene 5~10, styrene 5~10.
As a kind of perferred technical scheme, the modified acroleic acid ester material prepares raw material in parts by weight, including
Methyl methacrylate 40~45, butyl acrylate 15~20, butadiene 5~8, styrene 7~10.
As a kind of perferred technical scheme, the modified acroleic acid ester material is prepared by random copolymerization.
As a kind of perferred technical scheme, the random copolymerization preparation includes the following steps:
By butyl acrylate, butadiene and styrene in deionized water, half the weight of emulsifier, 1/3 in closed reactor
15min is stirred under the effect of weight initiator, reaction system is warming up to 65 DEG C, and reaction 30min obtains lotion I；
It takes methyl methacrylate to be add to deionized water, remaining emulsifier and 1/3 weight initiator is added, stir
15min is mixed, pre-emulsion is obtained；The temperature of I system of lotion is risen to 80 DEG C, and pre-emulsion is at the uniform velocity added dropwise in lotion I, is stirred
Reaction 45min is mixed, then adds remaining initiator, the pH value of sodium bicarbonate regulation system is added after reaction 2 hours to 7~8,
It discharges to obtain the final product.
As a kind of perferred technical scheme, the raw material for preparing of the modified acroleic acid ester material further includes 3~5 parts by weight
Activated monomer.
As a kind of perferred technical scheme, double bond and hydrophilic radical are contained on the activated monomer molecule.
As a kind of perferred technical scheme, the raw material for preparing of the modified acroleic acid ester material further includes 4~7 parts by weight
Crown ether-like monomer.
The second aspect of the present invention provides the application of above-mentioned modified acroleic acid ester material, is applied in manufacture optics device
Part.
The utility model has the advantages that modified acroleic acid ester material provided by the invention is in Charpy Impact, simply supported beam notch shock, cantilever
Beam impact, Izod notched impact, tensile break strength, elongation at break show excellent performance in testing, and have pole
Good toughness and hardness, while reasonably being selected and being prepared by the raw material for preparing to modified material, the modification made
Acrylate material retains the characteristics such as its original high grade of transparency and low haze.In addition, modified acroleic acid ester material tool is very strong
Ageing-resistant performance, can satisfy product and non-aging requirement be used for a long time, improve the service life and running efficiency of instrument.
Specific embodiment
It is further clear, complete that the technical characteristic work in technical solution is provided to the present invention With reference to embodiment
Description, not to the limitation of its protection scope.
Copolymer refers to the polymerization reaction participated in jointly by two or more monomer, claims combined polymerization, is formed by poly-
It closes object and contains two or more monomeric unit, this quasi polymer is known as copolymer and is also known as copolymer.
Word " preferred ", " preferably ", " preferred " in the present invention etc. refer to, can provide certain in some cases
The embodiment of the present invention of a little beneficial effects.However, other embodiments may also under identical circumstances or in the case of other
It is preferred.In addition, not implying that other embodiments are unavailable to the statement of one or more preferred embodiments, it is not yet
It is intended to exclude other embodiments except the scope of the present invention.
In order to solve the above-mentioned technical problem, the first aspect of the present invention provides a kind of modified acroleic acid ester material, described
The raw material for preparing of modified acroleic acid ester material includes methyl methacrylate, butyl acrylate, butadiene, styrene.
Methyl methacrylate is also known as MMA, abbreviation first methyl esters, and CAS 80-62-6 can be copolymerized with other monomers and prepare
Obtain product of different nature.Butyl acrylate (No. CAS: 141-32-2) is a kind of colorless and transparent liquid, can with homopolymerization, altogether
Poly- and graft copolymerization, high molecular polymer monomer are used as organic synthesis intermediate.There is longer alkyl chain in strand, make
Strand has certain flexibility.Butadiene is a kind of alkadienes, and the butadiene in the present invention is 1,3 butadiene, and No. CAS is
The double bond of 106-99-0,1,3 butadiene are more longer than general C=C double bond, and singly-bound is shorter than general C -- C single bond, and C-
The bond distance of H key is shorter than in butane, there is conjugation, and the polymer for being that the monomers tool such as methyl methacrylate obtains has
Certain flexibility.Styrene is the organic compound formed with a hydrogen atom of benzene substituted ethylene, the electronics and benzene of vinyl
Ring is conjugated, and has benzene ring structure in the strand, rigidity is larger, and the polymer flexibility that homopolymerization obtains is smaller.
In the modified acroleic acid ester material being prepared, the type difference for preparing monomer can cause resulting materials anti-
The performances such as impact property, transparency, intensity.The wherein methyl methacrylate segment part in polymer, due to containing on side chain
There is methylester portion, the interior rotation of strand receives influence, and the flexible of polymer material is caused to reduce, and material is made to become more crisp.Together
When, due to containing methyl esters group on polymer molecular chain, leads to the reduction of polymer regularity, make the degree of randomness of polymer molecular chain
Increase, polymer is caused to become more transparent.In addition, above-mentioned monomer in carrying out radical polymerization process due to monomer autohemagglutination and
The presence of Reactivity Ratio between multiple monomers makes the ratio of wherein monomer also can largely influence every object of material
Physicochemical performance.
In some embodiments, the molal weight of the methyl methacrylate is greater than or equal to, the butadiene with
The sum of the molal weight of the butyl acrylate；Preferably, the modified acroleic acid ester material prepares raw material, with parts by weight
Meter, including methyl methacrylate 35~50, butyl acrylate 15~20, butadiene 5~10, styrene 5~10；It is further excellent
Choosing, the modified acroleic acid ester material prepares raw material in parts by weight, including methyl methacrylate 40~45, acrylic acid
Butyl ester 15~20, butadiene 5~8, styrene 7~10.
In some embodiments, the modified acroleic acid ester material is prepared by random copolymerization；Preferably, institute
Random copolymerization preparation is stated to include the following steps:
By butyl acrylate, butadiene and styrene in deionized water, half the weight of emulsifier, 1/3 in closed reactor
15min, reaction system are stirred under weight initiator (i.e. the dosage of emulsifier accounts for the 1/3 of total emulsifiers weight herein) effect
65 DEG C are warming up to, reaction 30min obtains lotion I；
It takes methyl methacrylate to be add to deionized water, remaining emulsifier and 1/3 weight initiator is added, stir
15min is mixed, pre-emulsion is obtained；The temperature of I system of lotion is risen to 80 DEG C, and pre-emulsion is at the uniform velocity added dropwise in lotion I, is stirred
Reaction 45min is mixed, then adds remaining initiator, the pH value of sodium bicarbonate regulation system is added after reaction 2 hours to 7~8,
It discharges to obtain the final product.
Heretofore described term " 1/3 weight initiator " refers to the 1/3 of initiator gross mass, such as " 1/3 weight is added
Initiator " refers to " be added 1/3 times of initiator total weight of initiator ", remaining term, such as " half weight ... " etc. is also
Indicate similar meaning.
Wherein any restriction is not carried out to the emulsifier, can select nonionic surface active agent and/or from
Subtype surfactant, the present invention in preferably using etc. weight neopelex and fatty alcohol polyoxyethylene ether
(AEO-9) obtained emulsifier is compounded, the dosage of the emulsifier is the 1.5wt% for preparing raw material monomer gross mass.It is described to draw
Hair agent does not carry out special restriction, can select potassium peroxydisulfate, sodium peroxydisulfate, ammonium persulfate, dibenzoyl peroxide, tertiary fourth
Base hydrogen peroxide, azodiisobutyronitrile, azobisisoheptonitrile etc., it is preferred to use potassium peroxydisulfate, dosage are to prepare raw material monomer
The 0.2wt% of gross mass.
In some embodiments, the modified acroleic acid ester material prepares the activity that raw material further includes 3~5 parts by weight
Monomer；Preferably, double bond and hydrophilic radical are contained on the activated monomer molecule；Preferably, the hydrophilic radical is selected from
One of hydroxyl, carboxyl, amino, imino group, sulfydryl are a variety of；It is further preferred that the activated monomer be direct-connected shape or
Branched monomer (not including cyclic monomer).
Activated monomer in the present invention is to contain to carry out free-radical polymerized unsaturated group and contain simultaneously on strand
Have the monomer of hydrophilic radical, can enumerate have N- (2- ethoxy) acrylamide, 2- Methacrylamide, acrylamide,
Triamido propylene, N- methyl -2- acrylamide, N- [2- (dimethylamino) ethyl] -2- methyl -2- acrylamide, N- isopropyl
Butylmethacrylamide, N- (three (methylol) methyl) acrylamide, 2- chloroacrylamide, 6- acrylamido caproic acid, N- (2-
Hydroxypropyl) -2- methyl -2- acrylamide, N- (2- amino-ethyl) acrylamide etc..
In some embodiments, the modified acroleic acid ester material prepares the crown ether that raw material further includes 4~7 parts by weight
Class monomer；Preferably, the crown ether-like monomer is selected from 2- (allyloxymethyl) -18- crown ether -6,4- vinyl benzo -18-
One of crown ether -6,4- acrylamido Benzo-18-crown-6 are a variety of.
The activated monomer and crown ether-like monomer of constant weight ratio, resulting modified acroleic acid ester material are used in the present invention
Mechanical strength, impact strength, scantling stabilization, ageing-resistant performance, processing performance etc. improved simultaneously, especially pass
System PMMA material shock resistance is significantly improved to the sensibility of notch, while remaining the bloom of traditional PMMA material
The optical properties such as damp degree, the high grade of transparency.The possible reason is the present invention in using crown ether-like monomer hydrophily cavity structure with
Hydrophilic monomer generates host-guest interaction, improves the crosslinking degree between polymer molecular chain, and this crosslinking is total to traditional
Valence link crosslinking is different, and this crosslinking can occur to be broken and be recombinated when material is by certain stress or environmental stimuli, thus
The energy such as the impact that absorbing material is subject to make material have excellent mechanical strength.
In addition, it is found by the applicant that also and not all crown ether-like monomer and activated monomer can generate host-guest interaction, with
This come improve gained modified acroleic acid esters material comprehensive performance.When applicant uses the lesser 15- crown ether -5 of cavity structure
When class monomer, the performances such as elongation at break, impact strength of discovery gained modified acroleic acid ester material are not obtained significantly
It is promoted, has the tendency that its shock resistance is made to be deteriorated instead.Secondly when applicant has ring using 2- vinyl -4- pyridine amine etc.
When the activated monomer of shape steric hindrance larger structure, do not find out that the comprehensive performance of gained modified acroleic acid ester material is mentioned comprehensively yet
Height is instead declined the transparency of material.Applicant speculates that the possible cause for generating above situation is, when crown ether-like monomer
When cavity structure is too small or hydrophilic monomer has cyclic annular or steric hindrance larger structure, between activated monomer and crown ether cavity
Contact be obstructed, cause the host-guest interaction between it to weaken, slippage when material stress or stimulation between strand is opposite to be held
Easily occur, and material weakens the absorbability of energy, shock wave etc., also results in material elongation at break, shock resistance strong
The performances such as degree, mechanical strength cannot significantly improve.Instead, the biggish knot of biggish annular rigid is introduced in material internal
Structure hinders the change of polymer molecule chain conformation, so that more crisp instead, its some comprehensive performance that material becomes.
In a preferred embodiment, the preparation of the modified acroleic acid ester material includes the following steps:
S01: butyl acrylate, styrene, crown ether-like monomer are add to deionized water, monomer weight and deionized water
Volume ratio is 1g:8mL, and the initiator of emulsifier and 1/3 weight that 1/3 weight is added is stirred 15min, needed for being then pressed into
The butadiene of amount keeps 2~4.5MPa of pressure in kettle, is stirred to react 30min；
S02: activated monomer and the emulsifier of 1/3 weight, the initiator of 1/3 weight and deionized water are mixed to get pre- cream
Liquid I, wherein monomer weight and deionized water volume ratio are 1g:8mL；By methyl methacrylate and remaining emulsifier, initiation
Agent and deionized water are mixed to get pre-emulsion II, and wherein monomer weight and deionized water volume ratio are 1g:8mL；
S03: being warming up to 80 DEG C for the reaction system of the first step, then by pre-emulsion I and pre-emulsion II respectively with 4~
The speed of 5.4mL/min and 2.5~3.5mL/min is at the uniform velocity added drop-wise in the reaction system of the first step, keep temperature of reaction kettle and
It in the case that pressure is constant, is stirred to react 2~3 hours, is cooled to room temperature, the pH value of sodium bicarbonate regulation system is added to 7, out
Material, washing are drying to obtain.
It is found by the applicant that preparing raw material monomer due to there is autohemagglutination and polymerization process, reaction temperature, pressure during the reaction
The parameters such as power and feed way have key effect to the structure of resulting polymers after reaction.Wherein due to crown ether-like monomer parent
The outer layer of rouge and hydrophilic inner cavity, cause its dissolubility very poor, are also difficult to obtain stable emulsion system, therefore conventional side
Crown ether-like content of monomer is few in the polymer that method is prepared, and its being unevenly distributed on polymer molecular chain, and because
Cause blocked rotation in polymer molecule that resulting polymers shock resistance is caused to reduce instead for its biggish cyclic structure, power
Learning intensity also will receive large effect.In addition, methyl methacrylate, butyl methacrylate, butadiene in monomer with
And the monomers such as styrene occur that reactivity ratio when free radical polymerization is all different, and the change of condition may will affect respectively in co-mixing system
Distribution consistency degree of a monomer on polymer molecular chain, reaction temperature, pressure and charging sequence are different from speed
The change that can lead to polymer molecule chain structure influences the comprehensive performance of final resulting modified acroleic acid esters material.
The second aspect of the present invention provides the application of above-mentioned modified acroleic acid ester material, is applied in manufacture optics device
Part.
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
Embodiment 1
Embodiment 1 provides a kind of modified acroleic acid ester material, and the modified acroleic acid ester material prepares raw material, with weight
Measure part meter, including methyl methacrylate 35, butyl acrylate 15, butadiene 5, styrene 5.
Above-mentioned modified acroleic acid ester material is prepared by random copolymerization, and preparation step includes:
By the desired amount of butyl acrylate, butadiene and styrene in 150 parts by weight of deionized water, one in closed reactor
It is stirred under half weight (as 0.45 parts by weight) emulsifier, the effect of 1/3 weight (as 0.04 parts by weight) initiator
15min, reaction system are warming up to 65 DEG C, and reaction 30min obtains lotion I；
It takes methyl methacrylate to be add to deionized water, remaining (as 0.45 parts by weight) emulsifier and 1/ is added
3 weight (as 0.04 parts by weight) initiator, is stirred 15min, obtains pre-emulsion；The temperature of I system of lotion is risen to 80
DEG C, and pre-emulsion is at the uniform velocity added dropwise in lotion I, it is stirred to react 45min, remaining (as 0.04 parts by weight) is then added and draws
Send out agent, the pH value that sodium bicarbonate regulation system is added after reaction 2 hours discharges to 7 to obtain the final product.
Wherein the emulsifier be etc. weight neopelex and fatty alcohol polyoxyethylene ether (AEO-9) compounding
Obtained emulsifier, dosage account for the 1.5wt% for preparing raw material monomer gross mass；The initiator is potassium sulfate, and dosage accounts for
Prepare the 0.2wt% of raw material monomer gross mass.
Embodiment 2
Embodiment 2 provides a kind of modified acroleic acid ester material, and the modified acroleic acid ester material prepares raw material, with weight
Measure part meter, including methyl methacrylate 50, butyl acrylate 20, butadiene 10, styrene 10.
Above-mentioned modified acroleic acid ester material is prepared by random copolymerization, and preparation step is same as Example 1.
Embodiment 3
Embodiment 3 provides a kind of modified acroleic acid ester material, and the modified acroleic acid ester material prepares raw material, with weight
Measure part meter, including methyl methacrylate 40, butyl acrylate 15, butadiene 5, styrene 7.
Above-mentioned modified acroleic acid ester material is prepared by random copolymerization, and preparation step is same as Example 1.
Embodiment 4
Embodiment 4 provides a kind of modified acroleic acid ester material, and the modified acroleic acid ester material prepares raw material, with weight
Measure part meter, including methyl methacrylate 45, butyl acrylate 20, butadiene 8, styrene 10.
Above-mentioned modified acroleic acid ester material is prepared by random copolymerization, and preparation step is same as Example 1.
Embodiment 5
Embodiment 5 provides a kind of modified acroleic acid ester material, and the modified acroleic acid ester material prepares raw material, with weight
Measure part meter, including methyl methacrylate 42, butyl acrylate 16, butadiene 8, styrene 8.
Above-mentioned modified acroleic acid ester material is prepared by random copolymerization, and preparation step is same as Example 1.
Embodiment 6
Embodiment 6 provides a kind of modified acroleic acid ester material, and the modified acroleic acid ester material prepares raw material, with weight
Measure part meter, including methyl methacrylate 42, butyl acrylate 16, butadiene 8, styrene 8, Methacrylamide 3.
Above-mentioned modified acroleic acid ester material is prepared by random copolymerization, and preparation step includes:
S01: the butyl acrylate of required quality, styrene are add to deionized water, monomer weight and deionized water
Volume ratio is 1g:8mL, and the initiator of emulsifier and 1/3 weight that 1/3 weight is added is stirred 15min, needed for being then pressed into
The butadiene of amount keeps pressure 2MPa in kettle, is stirred to react 30min；
S02: Methacrylamide and the emulsifier of 1/3 weight, the initiator of 1/3 weight and deionized water are mixed to get
Pre-emulsion I, wherein monomer weight and deionized water volume ratio are 1g:8mL；By methyl methacrylate and remaining emulsifier,
Initiator and deionized water are mixed to get pre-emulsion II, and wherein monomer weight and deionized water volume ratio are 1g:8mL；
S03: being warming up to 80 DEG C for the reaction system of the first step, then by pre-emulsion I and pre-emulsion II respectively with 4mL/min
It is at the uniform velocity added drop-wise in the reaction system of the first step with the speed of 2.5mL/min, keeps temperature of reaction kettle and the constant situation of pressure
Under, it is stirred to react 2 hours, is cooled to room temperature, the pH value of sodium bicarbonate regulation system is added to 7, discharging, washing is drying to obtain.
Wherein the emulsifier be etc. weight neopelex and fatty alcohol polyoxyethylene ether (AEO-9) compounding
Obtained emulsifier, dosage account for the 1.5wt% for preparing raw material monomer gross mass；The initiator is potassium sulfate, and dosage accounts for
Prepare the 0.2wt% of raw material monomer gross mass.
Embodiment 7
Embodiment 7 provides a kind of modified acroleic acid ester material, and the modified acroleic acid ester material prepares raw material, with weight
Measure part meter, including methyl methacrylate 42, butyl acrylate 16, butadiene 8, styrene 8, Methacrylamide 5.
Above-mentioned modified acroleic acid ester material is prepared by random copolymerization, and preparation step includes:
S01: the butyl acrylate of required quality, styrene are add to deionized water, monomer weight and deionized water
Volume ratio is 1g:8mL, and the initiator of emulsifier and 1/3 weight that 1/3 weight is added is stirred 15min, needed for being then pressed into
The butadiene of amount keeps pressure 4.5MPa in kettle, is stirred to react 30min；
S02: Methacrylamide and the emulsifier of 1/3 weight, the initiator of 1/3 weight and deionized water are mixed to get
Pre-emulsion I, wherein monomer weight and deionized water volume ratio are 1g:8mL；By methyl methacrylate and remaining emulsifier,
Initiator and deionized water are mixed to get pre-emulsion II, and wherein monomer weight and deionized water volume ratio are 1g:8mL；
S03: being warming up to 80 DEG C for the reaction system of the first step, then by pre-emulsion I and pre-emulsion II respectively with 5.4mL/
The speed of min and 3.5mL/min is at the uniform velocity added drop-wise in the reaction system of the first step, keeps temperature of reaction kettle and the constant feelings of pressure
It under condition, is stirred to react 3 hours, is cooled to room temperature, the pH value of sodium bicarbonate regulation system is added to 7, discharging, washing drying is
?.
Wherein the emulsifier be etc. weight neopelex and fatty alcohol polyoxyethylene ether (AEO-9) compounding
Obtained emulsifier, dosage account for the 1.5wt% for preparing raw material monomer gross mass；The initiator is potassium sulfate, and dosage accounts for
Prepare the 0.2wt% of raw material monomer gross mass.
Embodiment 8
Embodiment 8 provides a kind of modified acroleic acid ester material, and the modified acroleic acid ester material prepares raw material, with weight
Measure part meter, including methyl methacrylate 42, butyl acrylate 16, butadiene 8, styrene 8, Methacrylamide 5,4 weight
2- (the allyloxymethyl) -18- crown ether -6 of part.
Above-mentioned modified acroleic acid ester material is prepared by random copolymerization, and preparation step includes:
S01: by butyl acrylate, styrene, 2- (allyloxymethyl)-the 18- crown ether -6 of required quality (CAS:
It 84812-04-4) is add to deionized water, monomer weight and deionized water volume ratio are 1g:8mL, and the cream of 1/3 weight is added
The initiator of agent and 1/3 weight is stirred 15min, is then pressed into the desired amount of butadiene, keeps pressure 3.8MPa in kettle,
It is stirred to react 30min；
S02: Methacrylamide and the emulsifier of 1/3 weight, the initiator of 1/3 weight and deionized water are mixed to get
Pre-emulsion I, wherein monomer weight and deionized water volume ratio are 1g:8mL；By methyl methacrylate and remaining emulsifier,
Initiator and deionized water are mixed to get pre-emulsion II, and wherein monomer weight and deionized water volume ratio are 1g:8mL；
S03: being warming up to 80 DEG C for the reaction system of the first step, then by pre-emulsion I and pre-emulsion II respectively with 4.8mL/
The speed of min and 3.0mL/min is at the uniform velocity added drop-wise in the reaction system of the first step, keeps temperature of reaction kettle and the constant feelings of pressure
It under condition, is stirred to react 3 hours, is cooled to room temperature, the pH value of sodium bicarbonate regulation system is added to 7, discharging, washing drying is
?.
Wherein the emulsifier be etc. weight neopelex and fatty alcohol polyoxyethylene ether (AEO-9) compounding
Obtained emulsifier, dosage account for the 1.5wt% for preparing raw material monomer gross mass；The initiator is potassium sulfate, and dosage accounts for
Prepare the 0.2wt% of raw material monomer gross mass.
Embodiment 9
Embodiment 9 provides a kind of modified acroleic acid ester material, and the modified acroleic acid ester material prepares raw material, with weight
Measure part meter, including methyl methacrylate 42, butyl acrylate 16, butadiene 8, styrene 8, Methacrylamide 5,7 weight
2- (the allyloxymethyl) -18- crown ether -6 of part.
Above-mentioned modified acroleic acid ester material is prepared by random copolymerization, and preparation step includes:
S01: by butyl acrylate, styrene, 2- (allyloxymethyl)-the 18- crown ether -6 of required quality (CAS:
It 84812-04-4) is add to deionized water, monomer weight and deionized water volume ratio are 1g:8mL, and the cream of 1/3 weight is added
The initiator of agent and 1/3 weight is stirred 15min, is then pressed into the desired amount of butadiene, keeps pressure 3.8MPa in kettle,
It is stirred to react 30min；
S02: Methacrylamide and the emulsifier of 1/3 weight, the initiator of 1/3 weight and deionized water are mixed to get
Pre-emulsion I, wherein monomer weight and deionized water volume ratio are 1g:8mL；By methyl methacrylate and remaining emulsifier,
Initiator and deionized water are mixed to get pre-emulsion II, and wherein monomer weight and deionized water volume ratio are 1g:8mL；
S03: being warming up to 80 DEG C for the reaction system of the first step, then by pre-emulsion I and pre-emulsion II respectively with 4.8mL/
The speed of min and 3.0mL/min is at the uniform velocity added drop-wise in the reaction system of the first step, keeps temperature of reaction kettle and the constant feelings of pressure
It under condition, is stirred to react 3 hours, is cooled to room temperature, the pH value of sodium bicarbonate regulation system is added to 7, discharging, washing drying is
?.
Wherein the emulsifier be etc. weight neopelex and fatty alcohol polyoxyethylene ether (AEO-9) compounding
Obtained emulsifier, dosage account for the 1.5wt% for preparing raw material monomer gross mass；The initiator is potassium sulfate, and dosage accounts for
Prepare the 0.2wt% of raw material monomer gross mass.
Embodiment 10
Embodiment 10 provides a kind of modified acroleic acid ester material, and the modified acroleic acid ester material prepares raw material, with
Parts by weight meter, including methyl methacrylate 42, butyl acrylate 16, butadiene 8, styrene 8, N- (2- ethoxy) acryloyl
2- (the allyloxymethyl) -18- crown ether -6 of amine 5,7 parts by weight.
Above-mentioned modified acroleic acid ester material is prepared by random copolymerization, and preparation step includes:
S01: by butyl acrylate, styrene, 2- (allyloxymethyl)-the 18- crown ether -6 of required quality (CAS:
It 84812-04-4) is add to deionized water, monomer weight and deionized water volume ratio are 1g:8mL, and the cream of 1/3 weight is added
The initiator of agent and 1/3 weight is stirred 15min, is then pressed into the desired amount of butadiene, keeps pressure 3.8MPa in kettle,
It is stirred to react 30min；
S02: by N- (2- ethoxy) acrylamide (No. CAS: 7646-67-5) and the emulsifier of 1/3 weight, 1/3 weight
Initiator and deionized water be mixed to get pre-emulsion I, wherein monomer weight and deionized water volume ratio are 1g:8mL；By methyl
Methyl acrylate and remaining emulsifier, initiator and deionized water are mixed to get pre-emulsion II, wherein monomer weight and go from
Sub- water volume ratio is 1g:8mL；
S03: being warming up to 80 DEG C for the reaction system of the first step, then by pre-emulsion I and pre-emulsion II respectively with 4.8mL/
The speed of min and 3.0mL/min is at the uniform velocity added drop-wise in the reaction system of the first step, keeps temperature of reaction kettle and the constant feelings of pressure
It under condition, is stirred to react 3 hours, is cooled to room temperature, the pH value of sodium bicarbonate regulation system is added to 7, discharging, washing drying is
?.
Wherein the emulsifier be etc. weight neopelex and fatty alcohol polyoxyethylene ether (AEO-9) compounding
Obtained emulsifier, dosage account for the 1.5wt% for preparing raw material monomer gross mass；The initiator is potassium sulfate, and dosage accounts for
Prepare the 0.2wt% of raw material monomer gross mass.
Comparative example 1
Comparative example 1 provides a kind of modified acroleic acid ester material, and the modified acroleic acid ester material prepares raw material, with weight
Measure part meter, including methyl methacrylate 8, butyl acrylate 16, butadiene 8, styrene 8, N- (2- ethoxy) acrylamide
5,2- (the allyloxymethyl) -18- crown ether -6 of 7 parts by weight.
Above-mentioned modified acroleic acid ester material is prepared by random copolymerization, and preparation step is same as Example 9.
Comparative example 2
Comparative example 2 provides a kind of modified acroleic acid ester material, and the modified acroleic acid ester material prepares raw material, with weight
Measure part meter, including methyl methacrylate 42, butyl acrylate 16, butadiene 8, styrene 8, Methacrylamide 5,7 weight
The 4- vinyl benzo -15- crown ether -5 (No. CAS: 39557-70-5) of part.
Above-mentioned modified acroleic acid ester material is prepared by random copolymerization, and preparation step is same as Example 9.
Comparative example 3
Comparative example 3 provides a kind of modified acroleic acid ester material, and the modified acroleic acid ester material prepares raw material, with weight
Measure part meter, including methyl methacrylate 42, butyl acrylate 16, butadiene 8, styrene 8,2- vinyl -4- pyridine amine
2- (the allyloxymethyl) -18- crown ether -6 of (No. CAS: 102000-57-7) 5,7 parts by weight.
Above-mentioned modified acroleic acid ester material is prepared by random copolymerization, and preparation step is same as Example 9.
Comparative example 4
Comparative example 4 provides a kind of modified acroleic acid ester material, and the modified acroleic acid ester material prepares raw material, with weight
Measure part meter, including methyl methacrylate 42, butyl acrylate 16, butadiene 8, styrene 8, Methacrylamide 5,25 weight
2- (the allyloxymethyl) -18- crown ether -6 of part.
Above-mentioned modified acroleic acid ester material is prepared by random copolymerization, and preparation step is same as Example 9.
Comparative example 5
Comparative example 5 provides a kind of modified acroleic acid ester material, and the modified acroleic acid ester material prepares raw material, with weight
Measure part meter, including methyl methacrylate 42, butyl acrylate 16, butadiene 8, styrene 8, Methacrylamide 25,7 weight
2- (the allyloxymethyl) -18- crown ether -6 of part.
Above-mentioned modified acroleic acid ester material is prepared by random copolymerization, and preparation step is same as Example 9.
Comparative example 6
Comparative example 6 provides a kind of modified acroleic acid ester material, and the modified acroleic acid ester material prepares raw material, with weight
Measure part meter, including methyl methacrylate 42, butyl acrylate 16, butadiene 8, styrene 8, Methacrylamide 5,7 weight
2- (the allyloxymethyl) -18- crown ether -6 of part.
Above-mentioned modified acroleic acid ester material is prepared by random copolymerization, and preparation step includes:
S01: by butyl acrylate, styrene, 2- (allyloxymethyl)-the 18- crown ether -6 of required quality (CAS:
It 84812-04-4) is add to deionized water, monomer weight and deionized water volume ratio are 1g:8mL, and the cream of 1/3 weight is added
The initiator of agent and 1/3 weight is stirred 15min, is then pressed into the desired amount of butadiene, keeps pressure 0.2MPa in kettle,
It is stirred to react 30min；
S02: Methacrylamide and the emulsifier of 1/3 weight, the initiator of 1/3 weight and deionized water are mixed to get
Pre-emulsion I, wherein monomer weight and deionized water volume ratio are 1g:8mL；By methyl methacrylate and remaining emulsifier,
Initiator and deionized water are mixed to get pre-emulsion II, and wherein monomer weight and deionized water volume ratio are 1g:8mL；
S03: being warming up to 80 DEG C for the reaction system of the first step, then by pre-emulsion I and pre-emulsion II respectively with 4.8mL/
The speed of min and 3.0mL/min is at the uniform velocity added drop-wise in the reaction system of the first step, keeps temperature of reaction kettle and the constant feelings of pressure
It under condition, is stirred to react 3 hours, is cooled to room temperature, the pH value of sodium bicarbonate regulation system is added to 7, discharging, washing drying is
?.
Wherein the emulsifier be etc. weight neopelex and fatty alcohol polyoxyethylene ether (AEO-9) compounding
Obtained emulsifier, dosage account for the 1.5wt% for preparing raw material monomer gross mass；The initiator is potassium sulfate, and dosage accounts for
Prepare the 0.2wt% of raw material monomer gross mass.
Comparative example 7
Comparative example 7 provides a kind of modified acroleic acid ester material, and the modified acroleic acid ester material prepares raw material, with weight
Measure part meter, including methyl methacrylate 42, butyl acrylate 16, butadiene 8, styrene 8, Methacrylamide 5,7 weight
2- (the allyloxymethyl) -18- crown ether -6 of part.
Above-mentioned modified acroleic acid ester material is prepared by random copolymerization, and preparation step includes:
S01: by butyl acrylate, styrene, 2- (allyloxymethyl)-the 18- crown ether -6 of required quality (CAS:
It 84812-04-4) is add to deionized water, monomer weight and deionized water volume ratio are 1g:8mL, and the cream of 1/3 weight is added
The initiator of agent and 1/3 weight is stirred 15min, is then pressed into the desired amount of butadiene, keeps pressure 3.8MPa in kettle,
It is stirred to react 30min；
S02: Methacrylamide and the emulsifier of 1/3 weight, the initiator of 1/3 weight and deionized water are mixed to get
Pre-emulsion I, wherein monomer weight and deionized water volume ratio are 1g:8mL；By methyl methacrylate and remaining emulsifier,
Initiator and deionized water are mixed to get pre-emulsion II, and wherein monomer weight and deionized water volume ratio are 1g:8mL；
S03: being warming up to 50 DEG C for the reaction system of the first step, then by pre-emulsion I and pre-emulsion II respectively with 4.8mL/
The speed of min and 3.0mL/min is at the uniform velocity added drop-wise in the reaction system of the first step, keeps temperature of reaction kettle and the constant feelings of pressure
It under condition, is stirred to react 3 hours, is cooled to room temperature, the pH value of sodium bicarbonate regulation system is added to 7, discharging, washing drying is
?.
Wherein the emulsifier be etc. weight neopelex and fatty alcohol polyoxyethylene ether (AEO-9) compounding
Obtained emulsifier, dosage account for the 1.5wt% for preparing raw material monomer gross mass；The initiator is potassium sulfate, and dosage accounts for
Prepare the 0.2wt% of raw material monomer gross mass.
Comparative example 8
Comparative example 8 provides a kind of modified acroleic acid ester material, and the modified acroleic acid ester material prepares raw material, with weight
Measure part meter, including methyl methacrylate 42, butyl acrylate 16, butadiene 8, styrene 8, Methacrylamide 5,7 weight
2- (the allyloxymethyl) -18- crown ether -6 of part.
Above-mentioned modified acroleic acid ester material is prepared by random copolymerization, and preparation step includes:
S01: by butyl acrylate, styrene, 2- (allyloxymethyl)-the 18- crown ether -6 of required quality (CAS:
It 84812-04-4) is add to deionized water, monomer weight and deionized water volume ratio are 1g:8mL, and the cream of 1/3 weight is added
The initiator of agent and 1/3 weight is stirred 15min, is then pressed into the desired amount of butadiene, keeps pressure 3.8MPa in kettle,
It is stirred to react 30min；
S02: Methacrylamide and the emulsifier of 1/3 weight, the initiator of 1/3 weight and deionized water are mixed to get
Pre-emulsion I, wherein monomer weight and deionized water volume ratio are 1g:8mL；By methyl methacrylate and remaining emulsifier,
Initiator and deionized water are mixed to get pre-emulsion II, and wherein monomer weight and deionized water volume ratio are 1g:8mL；
S03: being warming up to 80 DEG C for the reaction system of the first step, then at the uniform velocity drips pre-emulsion I with the speed of 4.8mL/min
It is added in the reaction system of the first step, then pre-emulsion II is directly added at one time in the reaction system and is mixed, protect
Hold temperature of reaction kettle and pressure it is constant in the case where, be stirred to react 3 hours, be cooled to room temperature, be added sodium bicarbonate regulation system
PH value to 7, discharging, washing is drying to obtain.
Wherein the emulsifier be etc. weight neopelex and fatty alcohol polyoxyethylene ether (AEO-9) compounding
Obtained emulsifier, dosage account for the 1.5wt% for preparing raw material monomer gross mass；The initiator is potassium sulfate, and dosage accounts for
Prepare the 0.2wt% of raw material monomer gross mass.
Comparative example 9
Comparative example 9 provides a kind of modified acroleic acid ester material, and the modified acroleic acid ester material prepares raw material, with weight
Measure part meter, including methyl methacrylate 42, butyl acrylate 16, butadiene 8, styrene 8, Methacrylamide 5,7 weight
2- (the allyloxymethyl) -18- crown ether -6 of part.
Above-mentioned modified acroleic acid ester material is prepared by random copolymerization, and preparation step includes:
S01: by butyl acrylate, styrene, 2- (allyloxymethyl)-the 18- crown ether -6 of required quality (CAS:
It 84812-04-4) is add to deionized water, monomer weight and deionized water volume ratio are 1g:8mL, and the cream of 1/3 weight is added
The initiator of agent and 1/3 weight is stirred 15min, is then pressed into the desired amount of butadiene, keeps pressure 3.8MPa in kettle,
It is stirred to react 30min；
S02: Methacrylamide and the emulsifier of 1/3 weight, the initiator of 1/3 weight and deionized water are mixed to get
Pre-emulsion I, wherein monomer weight and deionized water volume ratio are 1g:8mL；By methyl methacrylate and remaining emulsifier,
Initiator and deionized water are mixed to get pre-emulsion II, and wherein monomer weight and deionized water volume ratio are 1g:8mL；
S03: being warming up to 80 DEG C for the reaction system of the first step, then by pre-emulsion II with the speed of 3.0mL/min at the uniform velocity
It is added drop-wise in the reaction system of the first step, pre-emulsion I is directly added at one time in the reaction system and is mixed, keep anti-
It in the case where answering kettle temperature and pressure constant, is stirred to react 3 hours, is cooled to room temperature, the pH of sodium bicarbonate regulation system is added
To 7, discharging, washing is drying to obtain value.
Wherein the emulsifier be etc. weight neopelex and fatty alcohol polyoxyethylene ether (AEO-9) compounding
Obtained emulsifier, dosage account for the 1.5wt% for preparing raw material monomer gross mass；The initiator is potassium sulfate, and dosage accounts for
Prepare the 0.2wt% of raw material monomer gross mass.
Comparative example 10
Comparative example 10 provides a kind of modified acroleic acid ester material, and the modified acroleic acid ester material prepares raw material, with
Parts by weight meter, including methyl methacrylate 42, butyl acrylate 16, butadiene 8, styrene 8, Methacrylamide 5,7 weights
Measure 2- (the allyloxymethyl) -18- crown ether -6 of part.
Above-mentioned modified acroleic acid ester material is prepared by random copolymerization, and preparation step includes:
By -6 (CAS:84812- of butyl acrylate, styrene, 2- (allyloxymethyl) -18- crown ether of required quality
04-4), Methacrylamide, methyl methacrylate are add to deionized water, and monomer weight is with deionized water volume ratio
1g:8mL, is added all emulsifiers and initiator is stirred 15min, is then pressed into the desired amount of butadiene, keeps kettle internal pressure
Power 3.8MPa, is stirred to react 30min；Then reaction system is warming up to 80 DEG C, and keeps temperature of reaction kettle and pressure constant
In the case of, it is stirred to react 3 hours, is cooled to room temperature, the pH value of sodium bicarbonate regulation system is added to 7, discharging, washing drying is
?.
Wherein the emulsifier be etc. weight neopelex and fatty alcohol polyoxyethylene ether (AEO-9) compounding
Obtained emulsifier, dosage account for the 1.5wt% for preparing raw material monomer gross mass；The initiator is potassium sulfate, and dosage accounts for
Prepare the 0.2wt% of raw material monomer gross mass.
Performance evaluation
1. physical property measurement
A. Charpy Impact/notch impact strength is tested according to ISO-179/1eU, ISO-179/1eA, wherein anticipating without fracture
Taste material impact strength at least over 60KJ/m2More than；
B. Chalpy impact/notch impact strength is tested according to ISO-180, ISO-180/1A, wherein meaning without fracture
The impact strength of material is at least over 60KJ/m2More than；
C. according to ISO-13468/2 test light transmittance and mist degree；
Test data is as shown in table 1.
1 physical property measurement of table
2. mechanical performance
Tensile break strength/elongation at break, rate of extension 50mm/min are tested according to ISO-527；According to GB/T
Method described in 18950 carries out heat aging property test to embodiment and comparative example, at 160 DEG C of test after aging 72 hours
The relative change rate (%) of tensile break strength (MPa) and elongation at break (%), i.e., the value before value and aging after aging
Ratio (%), test data is as shown in table 2.
2 measuring mechanical property of table
In addition, " the odor detection company standard of PV3900-2000 " test is carried out to Examples 1 to 10, find
PMMA material can reach 3~3.5 grades, and wherein embodiment 8~10 may also reach up 2~2.5, and corresponding product is in use
Peculiar smell will not be generated, the injury to user is caused, influences usage experience sense.
As can be seen that modified acroleic acid ester material provided by the invention is in Charpy Impact, letter from above table 1~2
Strutbeam notch shock, Chalpy impact, Izod notched impact, tensile break strength, elongation at break are shown in testing
Excellent performance, has splendid toughness and hardness, at the same by modified material prepare raw material carry out reasonable selection and
Configuration, the modified acroleic acid ester material made retain the characteristics such as its original high grade of transparency and low haze.In addition, the modification third
Olefin(e) acid ester material has very strong ageing-resistant performance, can satisfy product and non-aging requirement is used for a long time, improve making for instrument
With service life and running efficiency.
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 acroleic acid ester material, which is characterized in that the raw material for preparing of the modified acroleic acid ester material includes methyl
Methyl acrylate, butyl acrylate, butadiene, styrene.
2. modified acroleic acid ester material as described in claim 1, which is characterized in that mole matter of the methyl methacrylate
Amount is greater than or equal to, the sum of the molal weight of the butadiene and the butyl acrylate.
3. modified acroleic acid ester material as described in claim 1, which is characterized in that the preparation of the modified acroleic acid ester material
Raw material, in parts by weight, including methyl methacrylate 35~50, butyl acrylate 15~20, butadiene 5~10, styrene 5
~10.
4. modified acroleic acid ester material as claimed in claim 3, which is characterized in that the preparation of the modified acroleic acid ester material
Raw material in parts by weight, including methyl methacrylate 40~45, butyl acrylate 15~20, butadiene 5~8, styrene 7~
10。
5. modified acroleic acid ester material as described in claim 1, which is characterized in that the modified acroleic acid ester material is to pass through
Random copolymerization is prepared.
6. modified acroleic acid ester material as claimed in claim 5, which is characterized in that the random copolymerization preparation includes following step
It is rapid:
By butyl acrylate, butadiene and styrene in deionized water, half the weight of emulsifier, 1/3 weight in closed reactor
15min is stirred under initiator effect, reaction system is warming up to 65 DEG C, and reaction 30min obtains lotion I；
It takes methyl methacrylate to be add to deionized water, remaining emulsifier and 1/3 weight initiator is added, is stirred
15min obtains pre-emulsion；The temperature of I system of lotion is risen to 80 DEG C, and pre-emulsion is at the uniform velocity added dropwise in lotion I, stirring is anti-
45min is answered, remaining initiator is then added, the pH value of sodium bicarbonate regulation system is added after reaction 2 hours to 7~8, discharges
To obtain the final product.
7. modified acroleic acid ester material as described in claim 1, which is characterized in that the preparation of the modified acroleic acid ester material
Raw material further includes the activated monomer of 3~5 parts by weight.
8. modified acroleic acid ester material as claimed in claim 7, which is characterized in that contain double bond on the activated monomer molecule
And hydrophilic radical.
9. modified acroleic acid ester material as claimed in claim 7, which is characterized in that the preparation of the modified acroleic acid ester material
Raw material further includes the crown ether-like monomer of 4~7 parts by weight.
10. the application of modified acroleic acid ester material as claimed in any one of claims 1 to 9 wherein, which is characterized in that be applied to
Manufacture optical device.
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| CN118440607A (en) * | 2023-10-24 | 2024-08-06 | 荣耀终端有限公司 | Protective film and electronic device |
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| CN105295280A (en) * | 2015-11-26 | 2016-02-03 | 长春工业大学 | Transparent rubber modified polymethyl methacrylate resin composition and preparation method thereof |
| US20160115309A1 (en) * | 2013-07-19 | 2016-04-28 | Lg Chem, Ltd. | (meth)acrylate-based resin composition having excellent impact resistance and transparency |
| CN106749850A (en) * | 2016-11-28 | 2017-05-31 | 苏州双象光学材料有限公司 | A kind of preparation method of damage resistant, high-impact PMMA materials |
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|---|---|---|---|---|
| CN102482016A (en) * | 2009-06-16 | 2012-05-30 | 电气化学工业株式会社 | Embossed carrier tape and method for manufacturing the same |
| US20160115309A1 (en) * | 2013-07-19 | 2016-04-28 | Lg Chem, Ltd. | (meth)acrylate-based resin composition having excellent impact resistance and transparency |
| CN105295280A (en) * | 2015-11-26 | 2016-02-03 | 长春工业大学 | Transparent rubber modified polymethyl methacrylate resin composition and preparation method thereof |
| CN106749850A (en) * | 2016-11-28 | 2017-05-31 | 苏州双象光学材料有限公司 | A kind of preparation method of damage resistant, high-impact PMMA materials |
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| CN118440607A (en) * | 2023-10-24 | 2024-08-06 | 荣耀终端有限公司 | Protective film and electronic device |
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