CN104072921A - Toughened polymethyl methacrylate mixture and preparation method thereof - Google Patents
Toughened polymethyl methacrylate mixture and preparation method thereof Download PDFInfo
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- CN104072921A CN104072921A CN201410308976.5A CN201410308976A CN104072921A CN 104072921 A CN104072921 A CN 104072921A CN 201410308976 A CN201410308976 A CN 201410308976A CN 104072921 A CN104072921 A CN 104072921A
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Abstract
The invention provides a toughened polymethyl methacrylate mixture which comprises the following components in percentage by weight: 90%-99.5% of PMMA (Polymethyl Methacrylate) and 0.5%-10% of PMMA-b-PBA-b-PMMA. The toughened polymethyl methacrylate mixture provided by the invention obviously enhances the impact strength of organic glass (by about 126% maximally), lowers the tensile strength by about 16% and keeps the transparency and heat-resistant property of the PMMA.
Description
Technical field
The invention belongs to chemical material field, relate to a kind of toughness reinforcing polymethylmethacrylate blend of acrylate triblock copolymer and preparation method thereof that utilizes.
Background technology
Polymethylmethacrylate (PMMA), is commonly called as synthetic glass, is a kind of important organic transparent material.It has excellent optical property, can see through more than 92% white light, and ultraviolet ray transmissivity also reaches more than 73%.Chemical stability, weathering resistance and electrical insulating property are good, and flexibility of operation is good, easily makes the transparent article of different shape and color.But its matter is crisp, and shock strength is low, is generally 16～18J/m, and there is notch sensitivity, in the time being applied to some occasion, need to carry out toughening modifying to meet shock resistance needs to it.
PMMA goods mainly contain two kinds of molding modes, and a kind of is the method production sheet material that is cast to again post polymerization in mould by body pre-polymerization in reactor.At this moment, can improve shock strength by the method for introducing flexible monomer copolymerization.As CN102127280A " a kind of toughening modifying synthetic glass method ", disclose and adopted Diisopropyl azodicarboxylate Methyl Methacrylate and butyl acrylate and add releasing agent to obtain the method for the toughness reinforcing synthetic glass of modification, but the introducing of butyl acrylate can reduce the second-order transition temperature of polymerisate, the texturing temperature of final sheet material is reduced.CN1113936C discloses " modified organic glass ", by adding softening agent, promotor Methyl Methacrylate and vinylbenzene, unsaturated polyester resin polymerization to obtain well behaved modified organic glass, its cost is low, but xanthochromia easily occurs for product weathering resistance and thermotolerance variation.CN101003669B " a kind of modified organic glass, variable color or light emissive plastic manufacture method and goods ", CN101724122A " preparing the method for copolymerized modified organic glass " and CN102690386A " a kind of preparation method of copolymerzation with cross-linking synthetic glass " disclose method by adding linking agent to improve the shock strength of synthetic glass, but the introducing of linking agent makes synthetic glass become thermosetting material, be not easy to be recycled.The alternative molding mode of PMMA is by extruding or the mode article of manufacture of injection moulding by commercialization plastic pellet (being commonly called as acrylic resin).Now, before moulding, can carry out toughening modifying to PMMA by traditional plastic blend mode.But toughening effect is good, easy to operate and can keep the transparent toughner of PMMA to lack very much always.
The granular acrylate triblock copolymer PMMA-b-PBA-b-PMMA that the present invention obtains by living polymerization with methyl methacrylate (MMA) and butyl acrylate (BA) and PMMA carry out melt blending to improve its shock strength, toughening effect is obvious, less on tensile strength and resistance toheat impact, be a kind of novel PMMA method for toughening.
Summary of the invention
The technical problem to be solved in the present invention is to provide good polymethylmethacrylate blend of a kind of over-all properties and preparation method thereof.
A toughness reinforcing polymethylmethacrylate blend, is grouped into by the one-tenth of following parts by weight:
Wherein, poly-(methyl methacrylate-b-butyl acrylate-b-methyl methacrylate) (PMMA-b-PBA-b-PMMA) triblock copolymer there is following structure:
Wherein X is halogen atom, and as F, Cl, Br, I, the ratio of halogen in PMMA is extremely low, and therefore halogen kind is very little on product performance impact;
Wherein, 359≤n≤664,25≤m≤80, molecular weight distribution≤1.5.
The PMMA adopting is commercially available acrylic resin, and molecular weight is 40000～60000.
The preparation method who the invention provides a kind of toughness reinforcing polymethylmethacrylate blend is to adopt following technique:
The material of said ratio is carried out to melt blending by Banbury mixer or twin screw extruder, impose a condition for Banbury mixer Temperature Setting be 175～200 DEG C, rotating speed is 100～200r/min, the melt blending time is 6～15 minutes, then on vulcanizing press, between 180 DEG C～200 DEG C, is pressed into smooth sheet material.
Or blending extrusion granulation obtains matrix material in parallel equidirectional two-screw forcing machine, 170～180 DEG C, its expressing technique Wei Yi district, two 180～190 DEG C, districts, three 190～200 DEG C, districts, four 190～200 DEG C, districts, screw speed 200～300r/min, feeding frequency 18～25Hz.Then on injection moulding machine in be injection molded into standard batten test performance between 190～200 DEG C.
Twin screw extruder in theory compared with Banbury mixer mix more even, but Banbury mixer mixed effect still can, so the finished product performance difference is also little.
The present invention compared with prior art, has following beneficial effect:
PMMA-b-PBA-b-PMMA optimum amount is 3%, and the shock strength (maximum has improved approximately 126%) that has obviously improved synthetic glass now tensile strength declines approximately 16%, and has kept transparency and the resistance toheat of PMMA.
Embodiment
Below by specific embodiment, the present invention is described in further detail, but the embodiment of the present invention is not limited to this.
Banbury mixer used is Haake Rheomix Banbury mixer.The twin screw extruder using is the SHJ-35 equidirectional parallel double-screw extruder of Nanjing Guang Da rubber and plastics machine factory, length-to-diameter ratio 40/1.Used test equipment comprises: universal tensile testing machine is the omnipotent drawing machine of TY-8000 type of Yangzhou Tian Yuan test machines company limited, is undertaken by ASTM D638 standard, and rate of extension is 5mm/min; Shock-testing machine is the TY-type of Yangzhou Tian Yuan experiment Machinery Co., Ltd., is undertaken by ASTM D256.The light transmission of synthetic glass is by the test of WGT-S type transmittance mist degree determinator, and according to GB2410-80 standard, thickness of sample is 3mm; Vicat softening point newly thinks carefully that by Shenzhen material detects the J302-7 type thermal distortion Vicat softening point test machine mensuration of company limited, is undertaken by GB/T1633-2000 standard, and temperature rise rate is 120 DEG C/h, and counterweight weight is 10N.
Wherein PMMA-b-PBA-b-PMMA triblock copolymer used is that this patent inventor synthesizes the product obtaining (as CN103374108 by active free radical polymerization, but be not limited to multipolymer prepared by the method, other industrial methods all can), molecular weight and distributed intelligence are in table 1.The PMMA resin adopting is LG chemistry, HI835H, molecular weight 42000.
Change respectively banburying temperature, rotating speed, banburying time, the press temperature of embodiment 1, observe the impact of parameter on final performance, test show to change product property indices that these parameters obtain all with the performance difference no difference of science of statistics of embodiment 1.Embodiment 11 adopts the preparation of twin screw extruder melt blending, finds that the product property indices that change processing parameter obtains does not have significant difference yet, and also there is no notable difference with product prepared by Banbury mixer.
Embodiment 2-7 changes the consumption of PMMA-b-PBA-b-PMMA, and other conditions are with embodiment 1, and performance test shows that PMMA-b-PBA-b-PMMA optimum amount is 3%, has obviously improved the shock strength of synthetic glass, and has kept transparency and the resistance toheat of PMMA.The consumption of embodiment 2 is slightly smaller than 0.5%, but performance and embodiment 1 differ greatly.
Embodiment 4,8,9,10 has used different PMMA-b-PBA-b-PMMA segmented copolymers, and other conditions are identical, when result shows to use the segmented copolymer II of embodiment 8, and best results.
The segmented copolymer of embodiment 12,13 is compared with segmented copolymer II (embodiment 8), PBA section is identical, PMMA section is not identical, the segmented copolymer of embodiment 14-16 is compared with segmented copolymer II (embodiment 8), PBA section difference, PMMA section is identical, and other conditions are identical, when result shows to use the segmented copolymer II of embodiment 8, best results.
Control group
50g PMMA pellet at 195 DEG C, is taken out after 100 turn/min banburying 10min in Banbury mixer, on vulcanizing press, be pressed into smooth sheet material in 190 DEG C.Make batten by relevant criterion and carry out notch shock test and Elongation test, performance is in table 2 and table 3.
Embodiment 1
The preparation of methacrylate sheet, preparation process is as follows:
After 49.75g PMMA pellet is mixed with 0.25g PMMA-b-PBA-b-PMMA I, in Banbury mixer at 180 DEG C, 100 turn/min banburying 10min are pressed into smooth sheet material in 185 DEG C on vulcanizing press.Make batten by relevant criterion and carry out notch shock test and Elongation test, performance is in table 2.
Embodiment 11
After 970g PMMA pellet is mixed with 30g PMMA-b-PBA-b-PMMA IV, in parallel equidirectional two-screw forcing machine, extruding pelletization obtains modified PMMA, 180 DEG C, its expressing technique Wei Yi district, two 185 DEG C, districts, three 190 DEG C, districts, four 195 DEG C, districts, turn/min of screw speed 280, feeding frequency 25Hz is then pressed into smooth sheet material in 190 DEG C on vulcanizing press.Make batten by relevant criterion and carry out notch shock test and Elongation test, performance is in table 2.
Molecular weight and the distribution of table 1PMMA-b-PBA-b-PMMA
The mechanical property of table 2PMMA-b-PBA-b-PMMA modified PMMA
Light transmission and the Vicat softening point of table 3PMMA-b-PBA-b-PMMA modified PMMA
As can be seen from the above data, add after the PMMA-b-PBA-b-PMMA of different content, the shock strength of PMMA obviously improves, and tensile strength and transmittance slightly decline, and Vicat softening point is almost constant.
Claims (4)
1. a toughness reinforcing polymethylmethacrylate blend, is grouped into by the one-tenth of following parts by weight:
2. polymethylmethacrylate blend claimed in claim 1, is characterized in that PMMA-b-PBA-b-PMMA triblock copolymer has following structure:
Wherein X is halogen atom, as F, Cl, Br, I;
Wherein, 359≤n≤664,25≤m≤80, molecular weight distribution≤1.5.
The PMMA adopting is commercially available acrylic resin, and molecular weight is 40000～60000.
3. polymethylmethacrylate blend claimed in claim 1, the parts by weight that it is characterized in that PMMA-b-PBA-b-PMMA triblock copolymer are 3%.
4. polymethylmethacrylate blend claimed in claim 1, is characterized in that
Three blocks of PMMA-b-PBA-b-PMMA triblock copolymer consist of PMMA6 × 10
3g/mol, PBA53 × 10
3g/mol, PMMA6 × 10
3g/mol.
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| CN201410308976.5A CN104072921A (en) | 2014-07-01 | 2014-07-01 | Toughened polymethyl methacrylate mixture and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107177152A (en) * | 2017-04-27 | 2017-09-19 | 蚌埠承永玻璃制品有限公司 | A kind of anti-crazing high tenacity lucite and preparation method thereof |
| CN110669178A (en) * | 2019-10-12 | 2020-01-10 | 江苏景泰玻璃有限公司 | Modified polymethyl methacrylate organic glass raw material and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102112433A (en) * | 2008-05-30 | 2011-06-29 | 阿克马法国公司 | Biomass-derived methyl methacrylate and corresponding manufacturing method, uses and polymers |
| CN103374108A (en) * | 2013-07-26 | 2013-10-30 | 常州大学 | Preparation method of triblock acrylic acid ester thermoplastic elastomer |
-
2014
- 2014-07-01 CN CN201410308976.5A patent/CN104072921A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102112433A (en) * | 2008-05-30 | 2011-06-29 | 阿克马法国公司 | Biomass-derived methyl methacrylate and corresponding manufacturing method, uses and polymers |
| CN103374108A (en) * | 2013-07-26 | 2013-10-30 | 常州大学 | Preparation method of triblock acrylic acid ester thermoplastic elastomer |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107177152A (en) * | 2017-04-27 | 2017-09-19 | 蚌埠承永玻璃制品有限公司 | A kind of anti-crazing high tenacity lucite and preparation method thereof |
| CN110669178A (en) * | 2019-10-12 | 2020-01-10 | 江苏景泰玻璃有限公司 | Modified polymethyl methacrylate organic glass raw material and preparation method thereof |
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Application publication date: 20141001 |