CN1752118A - Polymer using methyl methacrylate as main component - Google Patents
Polymer using methyl methacrylate as main component Download PDFInfo
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- CN1752118A CN1752118A CN 200410079890 CN200410079890A CN1752118A CN 1752118 A CN1752118 A CN 1752118A CN 200410079890 CN200410079890 CN 200410079890 CN 200410079890 A CN200410079890 A CN 200410079890A CN 1752118 A CN1752118 A CN 1752118A
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Abstract
A polymer containing perspex as its main component features that the content of its syndiotactic structure is 55 mole% and its weight decreasing temp is 290 deg.C or higher for the 5 Wt%. Its advantage is high resistance to thermocracking and high temp.
Description
Technical field
The present invention be a kind of be the polymkeric substance of principal constituent with methyl methacrylate (Methyl methacrylate), it has higher heat-resisting cracking temperature and heat resisting temperature; That is when using methyl methacrylate polymer of the present invention, the resistance to thermal decomposition of its melt fabrication is preferable, and the spendable ceiling temperature of molding is higher, and physical strength is good.
Background technology
Polymethylmethacrylate (Polymethyl methacrylate) is a broad-spectrum polymkeric substance, because of having the good transparency and weathering resistance, therefore often be used to make the various optical modules or the people's livelihood consumer's goods, for example camera lens, eyeglass, automobile tail light, billboard etc.; And because general glass can increase and the reduction transparency along with thickness, therefore need high-transmittance and big thickness to ensure structural safety at some, so that can't use the occasion of glass, for example aircraft windows, the large-scale display slot in aquarium etc., the material that polymethylmethacrylate is best suited for.
Though polymethylmethacrylate possesses above-mentioned excellent optical and weathering resistance, when machine-shaping, there is not heat-resisting cracking temperature good and use shortcoming such as thermotolerance deficiency.The polymethylmethacrylate of general industry production is to get with the polymerization of traditional free radical mode, about 105 ℃ of its glass tansition temperature (Glass transition temperature), and about 240～260 ℃ of the hot loss of weight temperature of 5 weight %, therefore in the use or add very big temperature limitation is arranged man-hour.For improving this shortcoming,, can in the Polymerization of Methyl reaction, add part acrylic acid methyl esters (Methyl acrylate) copolymerization usually, to improve the thermo-cracking stability according to the known technology of industry member.Close the generating capacity that only can reduce thermo-cracking but add methyl acrylate copoly, and can't effectively improve the beginning temperature of thermo-cracking; On the other hand, if add the too much fashionable glass tansition temperature that also can reduce polymethylmethacrylate of methyl acrylate copoly, make the use temperature of product limited.So polymethylmethacrylate of peddling on the open market, though major part is all the multipolymer that contains a small amount of methyl acrylate, its thermo-cracking begins temperature and still maintains 240～260 ℃, be more or less the same with polymethylmethacrylate (single polymers), therefore need be at some than the occasion of high processing temperature, when for example mixing mutually with other engineering plastics, its thermo-cracking begins temperature and still dislikes too low.
On the other hand, therefore advantage such as polycarbonate (Polycarbonate) is because possess dimensional stability, and impact strength and thermotolerance are good, and the transparency is good on a lot of optical Application Areass, comprises CD, all is the shaping material with the polycarbonate; But polycarbonate also has its shortcoming, for example scratch resistance (Scratch resistance) is poor, complex refractivity index under the stress (birefringence) difference is big, and its light transmission is also poor slightly than polymethylmethacrylate, therefore if can mixed polycarbonate and polymethylmethacrylate, be expected to merge both advantages and produce more suitable material.But general traditional polymethylmethacrylate is with after polycarbonate mixes, though can obtain favorable mechanical character, because of both specific refractory power differences, outward appearance is opaque shape.By U.S. Pat 5,280,070 disclosed content as can be known, the polymethylmethacrylate of tradition radical polymerization because of between to advise the content of (Syndiotactic) structure lower, therefore with after polycarbonate mixes to influence transparency, if syndiotactic structure can be improved, then can be improved with the mixed transparency of polycarbonate.In the present known technical field, when the polymethylmethacrylate of synthetic high syndiotactic structure, all with the catalyst of containing metal composition as its necessary polymerization catalyst composition, the lithium alkylide of anionoid polymerization (Alkyl lithium) for example, the alkyl magnesium halide of jesse greener reagent (Grignard reagent), the dialkyl magnesium (Dialkyl magnesium) of magnesium-vinegar amine (Amide) inductor catalyst and amine (Amine) resultant of reaction, or the triethyl aluminum (Triethylaluminum) of Z-N (Ziegler-Natta) catalyst and titanium tetrachloride catalyst such as (Titaniumtetrachloride).But need mostly when using these synthetic technologys under low temperature environment, for example the following temperature of zero centigrade can make high syndiotactic structure finished product.These methods are not easy and the cost height on producing, and therefore industrial so far also to carry out volume production with these technology, makes polymethylmethacrylate.
Summary of the invention
For addressing the above problem, the invention provides a kind of is the polymerization constituent of principal constituent with the polymethylmethacrylate, and it has good heat-resistant quality and thermotolerance, and syndiotactic structure content height, and easy industrialization volume production, the product physical strength is good, applicable to the general industrial commodity.
The present invention be a kind of be the polymkeric substance of principal constituent with the methyl methacrylate, it is characterized by:
A) number molecular-weight average 〉=50,000;
B) in nitrogen under the condition of 20 ℃/minute of heat-up rates, the temperature that weight reduces by 5 weight % is at least 290 ℃;
C) methyl methacrylate syndiotactic structure content is at least 55 moles of % (mol%) in the molecular arrangement;
D) the glass tansition temperature is at least 110 ℃.
Its general conventional polymeric products obtained therefrom have excellent heat-resistant quality (resistance to thermal decomposition), and the glass tansition temperature is higher, that is its processing temperature scope is bigger, and the end-use temperature scope is also bigger.
Polymerization single polymerization monomer of the present invention is principal constituent with the methyl methacrylate, that is can use other copolymerizable monomer of part and methyl methacrylate copolymer to close in the polymkeric substance of the present invention, wherein, methyl methacrylate can be 75～100 weight %, be preferably 85～100 weight %, be more preferred from 92～100 weight %.
Can there is no particular restriction with other copolymerizable monomer that methyl methacrylate copolymer closes in the present invention, so long as the polymerisable monomer of general traditional free radical all can, the preferably is for containing the compound of a vinyl at least, its content is generally 0～25 weight %, be preferably 0～15 weight %, be more preferred from 0～8 weight %, that wherein more common is styrenic monomers (Styrenic monomers), nitrilation vinyl monomer (Vinyl cyanide monomers), acrylic ester monomer (Acrylatemonomers), methacrylate ester monomer except the methyl methacrylate (Methacrylatemonomers other than methyl methacrylate), unsaturated vinegar amine is monomer (Unsaturatedamide monomers), vinyl acetate is monomer (Vinyl ester monomers), Malaysia vinegar imines is monomer (Maleimide monomers), diene monomer (Diene monomers), halogenation unsaturated monomer (Halogenated unsaturated monomers) and other polymerisable vinyl monomer.
Above-mentioned styrenic monomers is more common comprise vinylbenzene, alpha-methyl styrene, right-tributyl vinylbenzene, p-methylstyrene, neighbour-vinyl toluene ,-vinyl toluene, 2,4-dimethyl styrene, ethyl styrene, Alpha-Methyl-p-methylstyrene, right-sulfonic acid vinylbenzene or right-sulfonic acid vinylbenzene metal-salt, bromstyrol etc.; More common nitrilation vinyl monomer comprises vinyl cyanide, Alpha-Methyl vinyl cyanide etc.; More common acrylic ester monomer comprises methyl acrylate, ethyl propenoate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate (2-Ethylhexyl acrylate), dodecyl acrylate (Dodecyl acrylate), N, N-dimethyl aminoethyl acrylate (N, N-Dimethylaminoethyl acrylate), vinylformic acid 2-hydroxy methacrylate (2-hydroxyethyl acrylate), caprolactone denaturing acrylamide acid esters (Caprolactone modified acrylate), polyethylene glycol acrylate (Poly (ethylene glycol) acrylate) etc.; Methacrylate ester monomer except the more common methyl methacrylate comprises Jia Jibingxisuanyizhi, propyl methacrylate, butyl methacrylate, methacrylic acid 2-(ethyl hexyl) ester (2-Ethylhexyl methacrylate), methacrylic dodecyl gallate (Dodecyl methacrylate), N, N-dimethyl aminoethyl methacrylic ester (N, N-Dimethylaminoethyl methacrylate), 2-hydroxyethyl methacrylate (2-hydroxyethylmethacrylate), caprolactone sex change methacrylic ester (Caprolactone modifiedmethacrylate), polyethylene glycol methacrylate-styrene polymer (Poly (ethylene glycol) methacrylate) etc.; More common unsaturated vinegar amine is that monomer comprises acrylamide (Acrylamide), N, N-dimethyl allene vinegar amine (N, N-Dimethyl acrylamide), 2-acrylamide-2-methyl-propyl sulfonic acid (2-acrylamido-2-methylpropane sulfonic acid), the α of N-methylol acrylamide classes such as (N-Methylolacrylamide), the N-hydroxyalkyl vinegar amine (α of β-ethene unsaturated carboxylic acid, β-Ethylenic unsaturated carboxylic acid N-alkylol amide), methacrylic vinegar amine (Methacrylamide), N, N-dimethyl methyl acrylamide (N, N-Dimethyl methacrylamide), 2-acrylamide-2-methyl-propyl sulfonic acid (2-methacrylamido-2-methylpropane sulfonic acid), the α of N-methylol methacrylic vinegar amine classes such as (N-Methylolmethacrylamide), the N-hydroxyalkyl vinegar amine of β-ethene unsaturated carboxylic acid (α, β-Ethylenic unsaturated carboxylic acid N-alkylol amide) etc.; More common vinyl acetate is that monomer comprises vinyl acetate (Vinyl acetate), propionate (Vinylpropionate), vinyl neodecanoate (Vinyl versatate), pivalic vinyl acetate (Vinylpivalate) etc.; More common simple function Malaysia vinegar imines is that monomer comprises Malaysia vinegar imines (Maleimide), N-methyl Malaysia vinegar imines (N-Methyl maleimide), N-sec.-propyl Malaysia vinegar imines (N-Isopropyl maleimide), N-butyl Malaysia vinegar imines (N-butyl maleimide), N-hexyl Malaysia vinegar imines (N-hexyl maleimide), N-octyl group Malaysia vinegar imines (N-Octylmaleimide), N-dodecyl Malaysia vinegar imines (N-Dodecyl maleimide), N-cyclohexyl Malaysia vinegar imines (N-Cyclohexyl maleimide), N-phenyl Malaysia vinegar imines (N-phenylmaleimide), N-2-methylbenzene Malaysia vinegar imines (N-2-Methylphenyl maleimide), N-2,3-3,5-dimethylphenyl Malaysia vinegar imines (N-2,3-Dimethyl phenyl maleimide), N-2,4-3,5-dimethylphenyl Malaysia vinegar imines (N-2,4-Dimethyl phenyl maleimide), N-2,6-3,5-dimethylphenyl Malaysia vinegar imines (N-2,6-Dimethyl phenyl maleimide), N-2,3-diethyl phenyl Malaysia vinegar imines (N-2,3-Diethyl phenyl maleimide), N-2,4-diethyl phenyl Malaysia vinegar imines (N-2,4-Diethyl phenyl maleimide), N-2,3-dibutyl phenyl Malaysia vinegar imines (N-2,3-Dibutylphenyl maleimide), N-2,4-dibutyl phenyl Malaysia vinegar imines (N-2,4-Dibutyl phenylmaleimide), N-2,3-dichlorophenyl Malaysia vinegar imines (N-2,3-Dichlorophenyl maleimide), N-2,4-dichlorophenyl Malaysia vinegar imines (N-2,4-Dichlorophenyl maleimide), N-2,3-dibromo phenyl Malaysia vinegar imines (N-2,3-Dibromophenyl maleimide), N-2,4-dibromo phenyl Malaysia vinegar imines (N-2,4-Dibromophenyl maleimide) etc.; More common diene monomer comprises divinyl (Butadiene), isoprene (Isoprene), chloroprene (Chloroprene) etc.; More common halogenation unsaturated monomer comprises ethylene chloride (Vinyl chloride), ethylene fluoride (Vinylfluoride), vinylidene chloride (Vinylidene chloride), vinylidene fluoride (Vinylidenefluoride), inclined to one side sym-dibromoethane (Vinylidene bromide) etc.; Other more common polymerizable vinyl monomer still has ethene, vinylformic acid (Acrylic acid), methacrylic acid (Methacrylic acid), Maleic Acid, Anhydrous (Maleic anhydride), anhydrous methyl-maleic acid (Methyl maleicanhydride), FUMARIC ACID TECH GRADE (Fumaric acid), propylenedicarboxylic acid (Itaconic acid), dimethyl fumarate (Dimethyl fumarate), propylenedicarboxylic acid dibutylester (Dibutyl itaconate), the 3rd butylethylene ketone (tert-Butyl Vinyl Ketone) etc.
The polyreaction of polymethylmethacrylate of the present invention can body (Bulk) mode, solution (Solution) mode, emulsification (Emulsion) or outstanding turbid (Suspension) mode are carried out, when adopting the polymerization of solution mode, solvent for use there is no particular restriction, as long as can while dissolved monomer and polymkeric substance.Common solvent has benzene, toluene, ethylbenzene, p-Xylol, o-Xylol, m-xylene, pentane, hexane, hexanaphthene, heptane, octane, methylethylketone (Methyl ethyl ketone), acetone, methyl butyl ketone (Methyl butyl ketone), first isobutyl ketone (Methyl isobutyl ketone), N, N-dimethyl amide (N, N-Dimethylformamide, DMF), tetrahydrofuran (THF) Tetrahydrofuran) etc., can be independent or multiple during use and use.Can heat pressure reducing mode after the polyreaction, modes such as devolatilization groove or extruder are for example removed solvent and/or unreacted monomer, or with non-solvent (Non-solvent), and for example methyl alcohol etc. is incorporated in the polymers soln, makes polymkeric substance separate out recovery.When using emulsifying manner polymerization, system can add suitable interfacial agent, for example teepol (Anionic surfactants), cation interfacial active agent (Cationic surfactants), non-ionic surfactant (Nonionic surfactants), polyvinyl alcohol (Polyvinyl alcohol) etc.; Wherein common teepol has octylate (salts of caprylic acid), caprate (salts ofcapric acid), lauroleate (salts of lauric acid), myristate (salts of myristicacid), palmitate (salts of palmitic acid), stearate (salts of stearic acid), oleate (salts of oleic acid), linoleate (salts of linoleic acid), linolenate (salts oflinolenic acid), sylvate (salts of rosin acid), sweet potato hydrochlorate (salts of docosanoicacid), Viscotrol C sulfuric acid (sulfonated castor oil), lauryl alcohol sulfuric acid (laurylsulfate), ten diphenyl sulfonates (salts of dodecylbenzenesulfonic acid), sulfonated alkyl naphathalene (salts of alkylnaphthalenesulfonic acid), naphthalenesulfonate condensation compound (naphthalenesulfonates polycondensation) etc., above-mentioned said salt is meant that an alkali metal salt is (as lithium, sodium, potassium) or ammonium salt etc.; Common cation interfacial active agent has aliphatics amine salt (Alkylaminesalts), aliphatics ammonium salt (Alkylammoniumsalts), phenylmethane ammonium salt (Benzalkoniumsalts), pyridinium salt (Pyridinium salts); Common non-ionic surfactant has polyethylene oxide alkyl ethers (Polyoxyethylene alkyl ether), polyoxyethylene glycerol fatty acid ester (Polyoxyethylene glycerin fatty acid ester) etc., and all types of interfacial agent can be independent or multiple when using and use.
The present invention with the methyl methacrylate be the polymkeric substance of principal constituent be with the catalyst of containing metal composition not as the polymerization that becomes to assign to of the catalyst of necessity, preferable can the mode polymerization of control type free radical and get.So-called control type radical polymerization is meant that free radical carries out polymerization, and the active sustainable long-time existence of its free radical.In control type radical polymerization, free radical forms the sustainable reactive behavior of keeping in back, carry out polyreaction, it has following response characteristic, that is after the first reaction monomers polymerization finishes, has free radical activity in formed polymkeric substance one end of first reaction monomers, and after adding second reaction monomers, can be on the free radical of first polymkeric substance that reaction monomers forms, one end, continue polyreaction and form the polymkeric substance that is made of second reaction monomers, the polymkeric substance that aforementioned second reaction monomers is constituted is connected on the end of first polymkeric substance that reaction monomers becomes.So one of feature of control type free radical promptly is to add respectively to form segmented copolymer by monomeric batch.General traditional radical polymerization is after the first reaction monomers polymerization finishes, and an end of its polymkeric substance promptly no longer has free radical activity, and the adding of second reaction monomers also can't become to continue polyreaction on the polymkeric substance at first monomer.The concrete example of aforementioned control type free radical catalyst can be: use (i) interior vinegar aminated compounds, (ii) the control type free radical starter system of sulfur alcohol compound binary gained is that initiator (catalyst) carries out polyreaction, be preferably the interior vinegar aminated compounds of use (i), (ii) sulfur alcohol compound, (iii) the control type free radical starter system of free radical starting agent three composition gained.With above-mentioned control type free radical starter system is that the initiator polymerization gets, and more traditional thermopolymerization or the free radical starting agent of rule content is polymerized to height between its methyl methacrylate units.And it is that the molecular end pair keys of the polymethylmethacrylate that get of initiator polymerization are less that the contriver infers with control type free radical starter system, and this helps to improve the thermo-cracking temperature.Should be noted that, above-mentioned control type free radical starter system is only for giving an example, the present invention is not as limit, with other control type free radical mode polymerization, be that the polymkeric substance of principal constituent satisfies claim of the present invention as long as can make with the methyl methacrylate, have good heat-resistant quality and thermotolerance, and syndiotactic structure content height, and easy industrialization volume production, the product physical strength is good, all can applicable to intended purposes such as general industrial commodity.In the above-mentioned control type free radical starter system, interior vinegar aminated compounds is the compound of vinegar amine functional group in containing, and the carbonatoms of preferable interior vinegar amine ring is C
4～C
12Object lesson such as 2-Pyrrolidone (2-Pyrrolidinone), 1-Methyl-2-Pyrrolidone (1-Methyl-2-pyrrolidinone), 4-ethyl-2-pyrrolidone (4-Ethyl-2-pyrrolidinone), 3-ethyl-2-pyrrolidone (3-Ethyl-2-pyrrolidinone), N-(2-hydroxyethyl)-pyrrolidone (N-(2-hydroxyethyl)-pyrrolidinone), vinegar amine (2-Piperidinone) in penta, vinegar amine (3-Methyl-2-piperidinone) in 3-methyl-2-penta, 1, vinegar amine (1 in 5-dimethyl-2-penta, 5-Dimethyl-2-piperidinone), ε-vinegar amine in oneself (ε-Caprolactam), N-substituting group-ε-vinegar amine in oneself (N-Substituted-ε-Caprolactam), wherein substituting group can be methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, n-pentyl, isopentyl, phenyl methyl (C
6H
5CH
2-), beta-cyano ethyl (CN-CH
2-CH
2-), propionyloxy (HOOC-CH
2-CH
2-) etc., ω-Xin Nei vinegar the amine ((ω-Laurinlactam) etc. of vinegar amine in ω-Octalactam), ω-12 carbon.
The sulfur alcohol compound concrete example is the compound that comprises at least one thiol-functional base, and it is preferable for having C
2～C
25The alkyl segment, wherein, the alkyl segment can comprise alkyl (aliphatic), cycloalkyl (cycloaliphatic), aromatic base structures such as (aromatic), and aforesaid alkyl segment can further contain hydroxyl (HO-), carboxyl functional groups such as (HOOC-), object lesson such as normal-butyl mercaptan (n-Butylmercaptan), cyclohexyl mercaptan (Cyclohexyl mercaptan), n-octyl mercaptan (n-Octylmercaptan), n-dodecyl mercaptan (n-Dodecyl mercaptan), the 3rd-lauryl mercaptan (tert-Dodecyl mercaptan), 2-sulphur hydrogen ethyl n-caprylic acid ester (2-Mercaptoethyloctanoate), stearic mercaptan (Stearyl mercaptan), 2-sulphur ethanolic hydrogen (2-Mercaptoethanol), 3-sulphur hydrogen propionic acid (3-Mercaptopropionic acid), 3-sulphur hydrogen methyl propionate (Methyl 3-mercaptopropionate), 3-sulphur hydrogen propionic acid-2-(ethyl hexyl) ester (2-Ethylhexyl 3-mercaptopropionate), 3-sulphur hydrogen propionic acid-3-methoxyl group butyl ester (3-Methoxybutyl 3-mercaptopropionate), 3-sulphur hydrogen propionic acid three-ten esters (Tridecyl 3-mercaptopropionate), trimethylolpropane tris-3-mercaptopropionic acid ester (Trimethylolpropane tris-3-mercaptopropionate), tetramethylolmethane four-3-mercaptopropionic acid ester (Pentaerythritol tetrakis-3-mercaptopropionate), normal-butyl sulfo-glycolate (n-Butyl thioglycolate), 2-ethylhexyl sulfo-glycolate (2-Ethylhexyl thioglycolate), sulfo-glycolic acid ammonium (Ammoniumthioglycolate), benzyl mercaptan (Benzyl mercaptan), furfurylmercaptan (Furfuryl mercaptan), thiosalicylic acid (Thiosalicylic acid), 4-mercaptopyridine (4-Mercaptopyridine), 4-aminothiophenol (4-Aminothiophenol) etc.
Available free radical starting agent of the present invention there is no specific limited, object lesson has: azo compound, for example: 2,2 '-azobis isobutyronitrile (2,2 '-Azobis-(isobutyronitrile), be designated hereinafter simply as AIBN), 2, two (the 2-methylbutyronitriles) (2 of 2 '-azo, 2 '-Azobis-(2-methylbutyronitrile) is designated hereinafter simply as AMBN), 2,2 '-azo two (2, the 4-methyl pentane nitrile) (2,2 '-Azobis-(2,4-dimethylvaleronitrile), be designated hereinafter simply as ADVN) etc.; Peroxidation two vinegars (Diacyl peroxides) compounds, for example: peroxidation two bay vinegars (Dilauroyl peroxide), peroxidation 20 vinegars (Decanoyl peroxide), diphenyl peroxide first vinegar (Dibenzoyl peroxide is designated hereinafter simply as BPO) etc.; Peroxidation dioxane (Dialkyl peroxides) compounds, for example: 2,5-dimethyl-2,5-t-butyl peroxy hexane (2,5-Dimethyl-2,5-di-(t-butylperoxy) hexane), dicumyl peroxide (Dicumyl peroxide), 1, two (t-butyl peroxy sec.-propyl) benzene (1,3-Bis-(t-butyl peroxyisopropyl) benzene) of 3-etc.; Peroxyester (Peroxyesters) compounds, for example: t-butyl peroxy pivalate (t-butylperoxypivalate), 2,5-dimethyl-2,5-two (2-Ethylhexyl Alcohol peroxidation) hexane (2,5-Dimethyl-2,5-di (2-ethylhexanoylperoxy) hexane) etc.; Peroxycarbonates (peroxycarbonates) compounds, for example: 2-ethylhexyl t-amyl peroxy carbonic ether (tert-Amylperoxy 2-ethylhexyl carbonate), 2-ethylhexyl tert-butyl hydroperoxide carbonic ether (tert-Butylperoxy 2-ethylhexyl carbonate) etc.; Peroxy dicarbonate (peroxydicarbonates) compounds, for example: myristyl peroxy dicarbonate (Dimyristyl peroxydicarbonate), two (4-tert-butylcyclohexyl) (Di (4-tert-butylcyclohexyl) etc.; Peroxy ketal (Peroxyketal) compounds, for example: 3,3,5-trimethylammonium two (1,1-tert-butyl hydroperoxide ethane) (1,1-Di (tert-butylperoxy)-3,3,5-trimethylcyclohexane), 2,2-two (4,4-two (tert-butyl hydroperoxide) cyclohexyl) propane (2,2-Di (4,4-di (tert-butylperoxy) cyclohexyl) propane) etc.; Hydrogen peroxide (Hydroperoxides) compounds, for example: tertbutyl peroxide (t-Butyl hydroperoxide), sec.-propyl cumyl hydroperoxide (Isopropylcumyl hydroperoxide) etc.; Other, as 2,3-dimethyl-2,3-phenyl butane (2,3-Dimethyl-2,3-diphenyl-butane), Potassium Persulphate (Potassiumpersulfate), Sodium Persulfate (Sodium persulfate), ammonium persulphate (Ammonium persulfate) etc.; Wherein, the free radical starting agent that preferable is 10 hours half life temperatures are 20～120 ℃ is more preferred from 30～90 ℃.
Several compositions of the above control type free radical starter system can add respectively in the polymerization reaction system, also can be pre-mixed preparation, add in the polymerization reaction system and react.Can dissolution with solvents during preparation or type of heating make several composition uniform mixing.
For what try to achieve the good rerum natura of tool of the present invention is the polymkeric substance of principal constituent with the methyl methacrylate, the scope that above-mentioned sulfur alcohol compound consumption is general is to use 0.005～0.22 mole sulfur alcohol compound with respect to 100 moles of (mole) monomers, be preferably 0.01～0.18 mole, be more preferred from 0.03～0.11.The molar ratio of interior vinegar aminated compounds and sulfur alcohol compound was generally 0.4: 1.0～200: 1.0, was preferably 0.7: 1.0～150: 1.0, was more preferred from 0.9: 1.0～100: 1.0.The molar ratio of free radical starting agent and sulfur alcohol compound was generally 0.01: 1.0～10: 1.0, was preferably 0.02: 1.0～5.0: 1.0, was more preferred from 0.05: 1.0～3.0: 1.0.
Is the polymkeric substance of principal constituent for reaching of the present invention with the methyl methacrylate, and being preferably with the control type free radical system is that the initiator polymerization gets.For example (i) interior vinegar aminated compounds vinegar aminated compounds or (i), (ii) sulfur alcohol compound and (iii) free radical starting agent with (ii) sulfur alcohol compound.
When the usage quantity of sulfur alcohol compound, interior vinegar aminated compounds and free radical starting agent met above-mentioned scope, what can obtain to have following properties was the polymkeric substance of principal constituent with the methyl methacrylate:
(A) number molecular-weight average 〉=50,000;
(B) in nitrogen under the condition of 20 ℃/minute of heat-up rates, the temperature that weight reduces by 5 weight % is at least 290 ℃;
(C) methyl methacrylate syndiotactic structure content is at least 55 moles of % in the molecular arrangement;
(D) the glass tansition temperature is at least 110 ℃.
Particularly less when the usage quantity of sulfur alcohol compound, and the molar ratio of interior vinegar aminated compounds and sulfur alcohol compound is 0.4 when above.Furtherly, the use of cooperation free radical starting agent is reached more than 50,000 for the number molecular-weight average and is benefited to some extent.
Polyreaction can be carried out under normal temperature in the present invention, but for trying to achieve polymerization velocity faster, reactive system can be heated, and general temperature of reaction is about 5～200 ℃, and preferable temperature of reaction is 20～130 ℃, is more preferred from 30～100 ℃.The low person of temperature of reaction is that the polymkeric substance of principal constituent is more helpful with the methyl methacrylate for what obtain to have following properties, and particularly temperature of reaction is below 130 ℃:
(A) number molecular-weight average 〉=50,000;
(B) in nitrogen under the condition of 20 ℃/minute of heat-up rates, the temperature that weight reduces by 5 weight % is at least 290 ℃;
(C) methyl methacrylate syndiotactic structure content is at least 55 moles of % in the molecular arrangement;
(D) the glass tansition temperature is at least 110 ℃.
The present invention is the polymkeric substance of principal constituent with the methyl methacrylate, and its number molecular-weight average is at least 50,000, be preferably 50,000～250,000, be more preferred from 55,000～180,000, its Q value (weight average molecular weight/number molecular-weight average) generally there is no particular determination, is preferably 1.20～4.50, be more preferred from 1.25～3.20, the best is 1.30～2.80.When the number molecular-weight average is 50,000 or when above, the polymer machinery intensity of gained (is for example drawn Zhang Qiangdu, flexural strength etc.) good, the number molecular-weight average is 50,000 when following, and the polymer machinery undercapacity of gained is difficult for making the good moulding product of rerum natura with the working method on the general industry (for example ejection formation or extrusion molding).Secondly, the present invention is the polymkeric substance of principal constituent with the methyl methacrylate, and its glass tansition temperature is at least 110 ℃, is preferably 110～140 ℃, is more preferred from 115～130 ℃.When the glass tansition temperature more than 110 ℃ the time, the thermotolerance of polymkeric substance is good.The present invention is the polymkeric substance of principal constituent with the methyl methacrylate, and its methyl methacrylate syndiotactic structure content is at least 55 moles of %, is preferably 55～75 moles of %, is more preferred from 55～65 moles of %.Alleged syndiotactic structure among the present invention is with H
1Nuclear magnetic resonance spectrometer records, it is defined as: syndiotactic structure content=[rr/ (rr+mr+mm)] * 100%, wherein, rr represents between continuous three methyl methacrylate units formation and advises structure arranged, on behalf of continuous three methyl methacrylate units, mr form random (Atactic) structure arranged, and on behalf of continuous three methyl methacrylate units, mm form isotactic (Isotactic) structure arranged.For example in the occasion of methyl methacrylate list polymers, rr measures with the signal strength of chemical shift (Chemical shift) 0.82ppm, and mr measures with the signal strength of chemical shift 0.99ppm, and mm measures with the signal strength of chemical shift 1.18ppm.In addition, the present invention is the polymkeric substance of principal constituent with the methyl methacrylate, and under the condition of its 20 ℃/minute of heat-up rate in nitrogen, weight reduces at least 290 ℃ of the temperature of 5 weight %, is preferably 300～380 ℃, is more preferred from 310～360 ℃.Mensuration mode herein is to analyze gained with hot loss of weight analysis (Thermogravimetric analysis) instrument, during analysis sample placed hot loss of weight analyser, exist down in nitrogen, be warming up to 100 ℃ and continue 10 minutes to remove moisture, and with this moment weight be benchmark, speed with 20 ℃ of per minutes heats up then, can get hot loss of weight figure, and the temperature when weight reduces by 5 weight % is measured hot loss of weight temperature.In the present invention, be the polymkeric substance of principal constituent with the methyl methacrylate, advise structural content therebetween at 55 moles more than the %, and in nitrogen under the condition of 20 ℃/minute of heat-up rates, when weight reduced at least 290 ℃ of the temperature of 5 weight %, polymkeric substance had excellent heat-resistant quality (resistance to thermal decomposition) and thermotolerance (resistance to heat distorsion).
In addition, gained of the present invention be the polymkeric substance of principal constituent with the methyl methacrylate, can as the known application of polymethylmethacrylate, further other resin of blending, for example: polyvinyl chloride polymer, polystyrene-conjugated diene-acrylic copolymer, polystyrene-(methyl) acrylic ester-acrylic copolymer, polystyrene-(methyl) acrylate based copolymer, polystyrene-(methyl) acrylic ester-acrylic-Malaysia vinegar imines based copolymer, polystyrene-(methyl) acrylic ester-Malaysia vinegar imines based copolymer, (methyl) acrylic ester-Malaysia vinegar imines based copolymer, or with aforementioned multipolymer with the diene series rubber upgrading, for example: polystyrene-diolefin series-(methyl) acrylic ester-acrylic copolymer, polystyrene-diolefin series-(methyl) acrylate based copolymer, polystyrene-diolefin series-(methyl) acrylic ester-acrylic-Malaysia vinegar imines based copolymer, polystyrene-diolefin series-(methyl) acrylic ester-Malaysia vinegar imines based copolymer, (methyl) acrylic ester-diolefin series-Malaysia vinegar imines based copolymer etc.
The aforementioned resin usage quantity for respect to of the present invention be 0～200 weight part of polymkeric substance 100 weight parts of principal constituent with the methyl methacrylate, it can adjust or improve shock strength, thermotolerance, rigidity and the flow processability of resin according to need.
The present invention is the purposes of polymkeric substance of principal constituent and without particular limitation with the methyl methacrylate, its various moulding product, extrusion molding, blow and prolong the made finished product of moulding, thermoforming, vacuum forming and slush molding applicable to ejection formation, moulded section (Compression moulding), for example: give as security plate, film forming product etc., and can reach demands such as high workability, high heat resistance according to the prescription allotment.
The interpolation mixing of aforementioned other composition or resin can be mixed by the general mixing muller of Bradley Bender plastometer, Ban Baili muller, kneading-mixing machine, roller press, single shaft or twin shaft extruder etc. and be made.Usually after mixing by mixing such as these extruders; the extrusion thing of again signature being made is cooled off, granulation; above-mentioned mixing generally is to carry out under 160～280 ℃, and is good with 180～250 ℃ temperature, the mixing of respectively allocating composition again mix and out-of-order on special restriction.
Embodiment
Below cooperate the explanation of embodiment and comparative example, can clearly present technology contents of the present invention, characteristics and effect, but cited only is preferred embodiment, be not in order to limit patent claim of the present invention, all other do not break away from the equivalence of finishing under the disclosed spirit and changes, and all should comprise within the scope of the present invention.
The mensuration mode
Analytical procedure and condition that the present invention is used are as follows.
1. number molecular-weight average (Mn) and weight average molecular weight (Mw)
The polymkeric substance that will be principal constituent with the methyl methacrylate is dissolved in the solvent of tetrahydrofuran (THF), again with gel dialysis chromatograph (GPC, Waters corporate system) mensurations that performs an analysis, wherein, and is the polystyrene of the single distribution standard that performs an analysis with the molecular weight.The analysis condition of above-mentioned gel dialysis chromatograph is:
Tubing string 1 (Column1): American Polymer Standards Corporation 8680, TylerBlud Mentor, Ohio 4060;
Tubing string 2 (Column2): American Polymer Standards Corporation 8680, TylerBlud Mentor, Ohio 4060;
Analyzer: Waters 410,35 ℃ of temperature;
Mobile phase: THF, 1 ml/min.
2. transformation efficiency
Sampling and adding methyl alcohol termination reaction in the reaction process, gained weight is compared with the monomeric weight summation of former adding and is transformation efficiency after the drying.
3. glass tansition temperature
Use the DSC 2910 hot elementary errors scanning analysis instrument (Differential Scanning Calorimeter) of instrument as TA instruments.Sample thief places in the middle of the aluminium dish for 3～5 milligrams, under nitrogen environment, and control nitrogen flow rate 80 ml/min, 20 ℃/minute of temperature rise rates, scanning temperature range-40 ℃～200 ℃, glass transition point temperature is with the scanning curve decision second time.
4.5% weight loss temperature
Use instrument to be TA instruments TA-2100.Sample thief places platinum disc for 5～7 milligrams, and under nitrogen environment, the control nitrogen flow is 60 ml/min, 20 ℃/minute of temperature rise rates, and the scanning temperature is from 50 ℃～800 ℃.
5. methyl methacrylate syndiotactic structure content analysis
Use instrument to be Bruker Advanced 400 nuclear magnetic resonance spectrometers, H
1Resonant frequency be 400.13 megahertzes (MHz), with CDCl
3Be used as solvent, the polymethylmethacrylate sample be dissolved in wherein at room temperature measure.H
1Chemical shift is the internal standard product with TMS (Trimethyl silane).
Embodiment 1
With methyl methacrylate monomer as reaction monomers, it is repeated 2 purifying in the underpressure distillation mode after, in preserving below 5 ℃.
Get 100 milliliters of the methyl methacrylate monomers (0.93 mole) that purifying is crossed, 2,2 '-azobis isobutyronitrile, 0.02 gram (0.00012 mole), ε-vinegar amine 2.0 grams (0.018 mole) in oneself, and n-dodecyl mercaptan 0.05 gram (0.00025 mole), (mol ratio of above-mentioned free radical starting agent and sulfur alcohol compound=0.49: 1; The mol ratio of interior vinegar aminated compounds and sulfur alcohol compound=72: 1; And the mol ratio of sulfur alcohol compound and free radical polymerization monomer=0.027: 100), add down with in the glass reactor of whipping appts in nitrogen environment, pick up counting and carry out polyreaction, wherein above-mentioned glass reactor places tank in advance, bath temperature is 90 ℃, and sampling at set intervals after polymerization begins, add the methyl alcohol termination reaction after the sampling immediately, polymer precipitation is separated out, calculate transformation efficiency behind the oven dry weighing and further analyze its molecular weight, its data list is as follows.In addition, to analyze its glass tansition temperature with hot elementary errors scanning analysis instrument be 126 ℃ to 40 minutes oven dry finished product between negate was seasonable, the temperature of 5% weight loss is 337 ℃, and it is 57 moles of % that magnetic nuclear resonance analyzer (Nuclear MagneticResonance Spectroscopy) is analyzed syndiotactic structure content.
Table 1-embodiment 1
| Time (branch) | Transformation efficiency (weight %) | Mn | Mw/Mn |
| 10 | 4.1 | 158,500 | 1.7 |
| 20 | 8.3 | 198,600 | 1.8 |
| 30 | 12.5 | 254,300 | 1.8 |
| 40 | 15.9 | 290,300 | 1.7 |
Embodiment 2
With embodiment 1, the usage quantity of each composition is, 100 milliliters of methyl methacrylate monomers (0.93 mole), 2,2 '-azo two (2, the 4-methyl pentane nitrile), 0.05 gram (0.00020 mole), n-dodecyl mercaptan 0.12 gram (0.00059 mole), ε-vinegar amine 5.0 grams (0.044 mole) in oneself, bath temperature is 70 ℃, the data such as the table 2 of transformation efficiency and molecular weight.In addition, 60 minutes oven dry check analysis glass tansition temperature was 124 ℃ between negate was seasonable, and the temperature of 5% weight loss is 335 ℃, and syndiotactic structure content is 58 moles of %.
Table 2-embodiment 2
| Time (branch) | Transformation efficiency (weight %) | Mn | Mw/Mn |
| 5 | 5.0 | 57,100 | 1.6 |
| 10 | 9.6 | 59,980 | 1.7 |
| 40 | 34.7 | 64,570 | 1.5 |
| 60 | 48.4 | 69,120 | 1.8 |
Embodiment 3
With embodiment 1, the usage quantity of each composition is, 100 milliliters of methyl methacrylate monomers (0.93 mole), 2,2 '-azo two (2, the 4-methyl pentane nitrile), 0.03 gram (0.00020 mole), n-dodecyl mercaptan 0.07 gram (0.00035 mole), 2-Pyrrolidone 3 grams (0.035 mole), bath temperature is 80 ℃, the data such as the table 3 of transformation efficiency and molecular weight.In addition, 70 minutes oven dry check analysis glass tansition temperature was 125 ℃ between negate was seasonable, and the temperature of 5% weight loss is 335 ℃, and syndiotactic structure content is 59 moles of %.
Table 3-embodiment 3
| Time (branch) | Transformation efficiency (weight %) | Mn | Mw/Mn |
| 70 | 49.0 | 131,100 | 1.8 |
Comparative example 1
With embodiment 1, the usage quantity of each composition is, 100 milliliters of methyl methacrylate monomers (0.93 mole), and 2,2 '-azobis isobutyronitrile, 0.05 gram (0.00012 mole), bath temperature is 70 ℃, the data of transformation efficiency and molecular weight are as table C1.In addition, 40 minutes oven dry check analysis glass tansition temperature was 106 ℃ between negate was seasonable, and the temperature of 5% weight loss is 243 ℃, and syndiotactic structure content is 48 moles of %.
Table C1-comparative example 1
| Time (branch) | Transformation efficiency (weight %) | Mn | Mw/Mn |
| 40 | 51.8 | 98,240 | 4.7 |
Comparative example 2
With embodiment 1, the usage quantity of each composition is 100 milliliters of methyl methacrylate monomers (0.93 mole), 2-Pyrrolidone 12 grams (0.010 mole), and n-dodecyl mercaptan 0.23 gram (0.0011 mole), bath temperature is 90 ℃, the data of transformation efficiency and molecular weight are as table C2.In addition, 280 minutes oven dry check analysis glass tansition temperature was 124 ℃ between negate was seasonable, and the temperature of 5% weight loss is 334 ℃, and syndiotactic structure content is 58 moles of %.
Table C2-comparative example 2
| Time (branch) | Transformation efficiency (weight %) | Mn | Mw/Mn |
| 90 | 11.3 | 4,090 | 1.6 |
| 260 | 43.2 | 21,090 | 1.6 |
| 280 | 60.2 | 29,540 | 1.7 |
Comparative example 3
In the continous way processing procedure that is constituted by 2 continous way stirred reactors, with methyl methacrylate/methyl acrylate/AIBN/ toluene/n-dodecyl mercaptan is the ratio pan feeding of 0.96/0.041/0.00080/1.0/0.0012 with the mol ratio, in 100 ℃ of reactions down, 6 hours residence times, discharge port sampling analysis by the 2nd continous way stirred reactor, its transformation efficiency is 60.4 weight %, the number molecular-weight average is 98,600, the glass tansition temperature is 105 ℃, the temperature of 5% weight loss is 244 ℃, and syndiotactic structure content is 48 moles of %.
Embodiment 4
Reaction monomers is methyl methacrylate and vinylbenzene, the usage quantity of each composition is, 97 milliliters of methyl methacrylates (0.90 mole), 3 milliliters of vinylbenzene (0.026 mole), 2,2 '-azobis isobutyronitrile, 0.1 gram (0.00061 mole), n-dodecyl mercaptan 0.1 gram (0.00049 mole), ε-vinegar amine 2.0 grams (0.018 mole) in oneself carries out polyreaction with the method that is same as embodiment 1, and bath temperature is 80 ℃, the data such as the table 4 of transformation efficiency and molecular weight.In addition, 40 minutes oven dry check analysis glass tansition temperature was 124 ℃ between negate was seasonable, and the temperature of 5% weight loss is 336 ℃, and syndiotactic structure content is 58 moles of %.
Table 4-embodiment 4
| Time (branch) | Transformation efficiency (weight %) | Mn | Mw/Mn |
| 10 | 7.5 | 44,340 | 1.5 |
| 30 | 28.1 | 50,710 | 1.6 |
| 40 | 55.3 | 55,720 | 1.5 |
Embodiment 5
Reaction monomers is methyl methacrylate and methyl acrylate, the usage quantity of each composition is, 97 milliliters of methyl methacrylates (0.90 mole), 3 milliliters of methyl acrylates (0.033 mole), 2,2 '-azobis isobutyronitrile, 0.1 gram (0.00061 mole), n-dodecyl mercaptan 0.08 gram (0.00040 mole), ε-vinegar amine 2.0 grams (0.018 mole) in oneself carries out polyreaction with the method that is same as embodiment 1, and bath temperature is 80 ℃, the data such as the table 5 of transformation efficiency and molecular weight.In addition, 60 minutes oven dry check analysis glass tansition temperature was 124 ℃ between negate was seasonable, and the temperature of 5% weight loss is 335 ℃, and syndiotactic structure content is 58 moles of %.
Table 5-embodiment 5
| Time (branch) | Transformation efficiency (weight %) | Mn | Mw/Mn |
| 10 | 17.6 | 35,890 | 1.8 |
| 20 | 30.2 | 42,640 | 1.8 |
| 30 | 40.1 | 46,300 | 1.9 |
| 40 | 45.4 | 50,410 | 1.9 |
| 60 | 53.8 | 54,800 | 1.9 |
Embodiment 6
Fs: polymethyl methacrylate solution
With embodiment 1, the usage quantity of each composition is, 20 milliliters of methyl methacrylate monomers (0.19 mole), solvent N, N-dimethyl amide (N, N-Dimethylformamide, DMF) 100 milliliters, 2,2 '-azobis isobutyronitrile, 0.05 gram (0.00030 mole), n-dodecyl mercaptan 0.027 gram (0.00013 mole), ε-vinegar amine 1 gram (0.0088 mole) in oneself, bath temperature is 85 ℃, carry out polyreaction, sampling analysis after 48 hours, polymethylmethacrylate number molecular-weight average is 52,600 gram/moles, transformation efficiency are 99.1 weight %.
Subordinate phase: get above-mentioned polymethyl methacrylate solution 29.4 grams, add 20.0 gram (0.19 mole) styrene monomers again, bath temperature continues polyreaction for 80 ℃, sampling analysis after 30 minutes, number molecular-weight average are 55,310 gram/moles, molecular weight distribution Q value is 1.7, the glass tansition temperature is 124 ℃, and the temperature of 5% weight loss is 336 ℃, and syndiotactic structure content is 58 moles of %.
In addition, two stage gel dialysis chromatograph (Gel Permeation Chromatography, GPC) the molecular weight analyse figure is all single crest, and the molecular weight during the subordinate phase polymerization carries out with polyreaction and increases, and molecular weight distribution Q value still remains on 1.7, show that the styrene monomer that is added in the subordinate phase continues polymerization in the end of the methyl methacrylate monomer of fs, reaction gained person is methyl acrylate-styrenic diblock copolymer.In addition, the infrared spectrometer analysis also shows that the polymkeric substance of gained contains methyl methacrylate polymerization unit and styrene polymerization modular construction.
Claims (3)
1. one kind is the polymkeric substance of principal constituent with the methyl methacrylate, it is characterized by:
A) number molecular-weight average 〉=50,000;
B) in nitrogen under the condition of 20 ℃/minute of heat-up rates, the temperature that weight reduces by 5 weight % is at least 290 ℃;
C) methyl methacrylate syndiotactic structure content is at least 55 moles of % in the molecular arrangement;
D) the glass tansition temperature is at least 110 ℃.
2. described according to claim 1 is the polymkeric substance of principal constituent with the methyl methacrylate, it is characterized in that, is that the mode with the control type free radical is polymerized.
3. described according to claim 1 is the polymkeric substance of principal constituent with the methyl methacrylate, it is characterized in that polymethylmethacrylate content 〉=75 weight %.
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| FR2698630B1 (en) * | 1992-11-27 | 1995-01-06 | Atochem Elf Sa | Process for the preparation of thermoplastic elastomer block copolymers derived from conjugated dienes and from methyl methacrylate, with improved heat resistance and products obtained. |
| ES2166079T3 (en) * | 1996-05-10 | 2002-04-01 | Du Pont | ACRYLIC POLYMER COMPOUNDS. |
| FR2809741B1 (en) * | 2000-05-31 | 2002-08-16 | Atofina | IMPROVED SHOCK RESISTANT MATERIALS |
| CN1182166C (en) * | 2001-04-04 | 2004-12-29 | 北京大学 | Heat resistant organic glass |
| CN1463275A (en) * | 2001-05-23 | 2003-12-24 | 三井化学株式会社 | Methacrylic resin and use thereof |
| JP2002370324A (en) * | 2001-06-15 | 2002-12-24 | Mitsubishi Gas Chem Co Inc | Thermoplastic resin laminate |
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| CN112778130B (en) * | 2021-01-25 | 2023-05-16 | 江西省正百科技有限公司 | Organic glass recovery process |
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