CN102344537B - Block copolymer and polymer composition prepared with block copolymer - Google Patents
Block copolymer and polymer composition prepared with block copolymer Download PDFInfo
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- CN102344537B CN102344537B CN201010243512.2A CN201010243512A CN102344537B CN 102344537 B CN102344537 B CN 102344537B CN 201010243512 A CN201010243512 A CN 201010243512A CN 102344537 B CN102344537 B CN 102344537B
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Abstract
The invention relates to a block copolymer and a polymer composition prepared with the block copolymer. The block copolymer comprises a first block and a second block. The first block comprises monomeric units containing epoxy groups, and acrylate monomeric units or methacrylate monomeric units or a combination of acrylate monomeric units and methacrylate monomeric units; the second block comprises styrene monomeric units. Epoxy equivalent weight of the block copolymer is 1000g/equivalent weight to 20000g/equivalent weight, and molecular weight distribution index of the block copolymer is 1.0 to 2.0. The invention also provides a polymer composition prepared with the block copolymer.
Description
Technical field
The present invention relates to a kind of segmented copolymer of active free radical polymerization, refer to especially a kind of segmented copolymer that comprises epoxy group(ing), and a kind of polymer composition making with it.
Background technology
Because the Application Areas of polymer composition is more and more wide, and along with the demand of Different Industries, for polymer property, also there is different requirements, so people constantly develop various new polymerss, with the mixed type polymer in conjunction with different types of resin, receive much concern, because mixed type polymer can be in conjunction with the characteristic of each composition resin, for example cost is lower, physical strength is higher or biodegradable etc. advantage, therefore can be more suitable for various specific end use.
For example, the mixed type polymer that use comprises styrene-acrylonitrile-butadiene polymkeric substance (ABS) and polymethylmethacrylate (PMMA), replace pure styrene-acrylonitrile-butadiene copolymers, just can reduce the usage quantity of expensive polymkeric substance, to reach the object reducing costs.For example use again the mixed type polymer that comprises poly(lactic acid) (PLA) and vinylbenzene (PS) to replace pure styrene polymkeric substance, not only can reduce the use of petroleum resources to reduce carbon emission, and PLA is Biodegradable polymkeric substance, therefore also there is the advantages such as the pollution of minimizing.In addition, polyester polymer, such as p-poly-phenyl dioctyl phthalate ethyl ester (PET) etc. is often used to bottled drink, if can reclaim and with other mixed with polymers, and then become a useful shaped material, and can reduce refuse production on the one hand, there is again on the one hand economic benefit.
But, because the chemical structure of different polymkeric substance and characteristic difference cause having compatibility problem between the different types of polymkeric substance in mixed type polymer, so the development technique of compatibility agent has become the crucial emphasis of field development for this reason.
For example, a kind of way of known technology is that the ethene that interpolation comprises unsaturated acid glycidyl ester monomer unit in the mixed polymer of styrenic and aliphatic polyester is that copolymer is as compatibility agent at present, but because this kind of compatibility agent belongs to random copolymerization zoarium but not block copolymerization zoarium, and not use living radical polymerization synthetic, its molecular weight distribution is wider, and therefore the mechanical properties of its prepared mixed polymer constituent does not meet industry actual demand.
In addition, still have and in the mixed polymer of vinylbenzene (styrene) based polymer and polymer in poly lactic acid series, add the way of polystyrene-(methyl) acrylic ester block copolymerization zoarium as compatibility agent.
But, compatibility agent in aforesaid method is only to bring into play compatibilized effect by the affinity between different blocks and each composition polymkeric substance, between compatibility agent and each composition polymkeric substance, do not have chemical bonded refractory, therefore, the mechanical properties of its prepared mixed polymer constituent, for example shock strength, although promote to some extent compared to the mixed polymer constituent that does not add compatibility agent, but still have amendatory space, and, above-mentioned way only limits to the mixed stocker polymkeric substance that styrenic and polymer in poly lactic acid series form, and range of application is limited to.
Therefore, still have at present and need to develop a kind of compatibility agent that can promote consistency between different polymeric constituents, and the good polymer composition of a kind of mechanical properties making with it.
Summary of the invention
Because present inventor finds the mechanical properties of polymer composition, whether the different types of polymeric constituent forming with it can mix great relation, that is to say, consistency between different types of polymeric constituent can have influence on the mechanical properties of polymer composition, therefore, contriver just sets about from used compatibility agent, and through repeatedly studying discovery, when the molecular weight distributing index of this compatibility agent is between 1.0 to 2.0, and its epoxy equivalent (weight) is between 1, 000 gram/equivalent to 20, in the time of between 000 gram/equivalent, under identical dosage, the shock strength of the polymer composition making can have greatly improved.
Therefore, the first object of the present invention is to provide a kind of segmented copolymer that can promote consistency between different polymeric constituents.
So, segmented copolymer of the present invention comprises the first block and the second block, this first block comprises monomeric unit and this first block with epoxy group(ing) and comprises acrylic ester monomeric unit, or methacrylate ester monomeric unit, or the combination of acrylic ester monomeric unit and methacrylate ester monomeric unit; This second block comprises styrenic monomers unit, and the epoxy equivalent (weight) of this segmented copolymer is between 1,000 gram/equivalent to 20, and between 000 gram/equivalent, its molecular weight distributing index is between 1.0 to 2.0.
Therefore, the second object of the present invention is to provide the good polymer composition of a kind of shock strength.
Polymer composition of the present invention comprises following component: styrenic, non-styrenic and segmented copolymer as above, and this non-styrenic be selected from can with the polymkeric substance of epoxy reaction, methacrylate ester polymkeric substance, acrylic ester polymer, or the combination of described polymkeric substance.
Beneficial effect of the present invention is: the present invention uses the segmented copolymer with specified molecular weight dispersion index and epoxy equivalent (weight) scope as compatibility agent, by the epoxy group(ing) in compatibility agent, make the consistency between different types of polymeric constituent better, and then the mechanical properties of lifting polymer composition, therefore really can reach beneficial effect of the present invention.
Accompanying drawing explanation
Fig. 1 is a TEM figure, shows the configuration of surface of the test piece forming with the polymer composition of embodiment 11;
Fig. 2 is a TEM figure, shows the configuration of surface of the test piece forming with the polymer composition of embodiment 15;
Fig. 3 is a TEM figure, shows the configuration of surface of the test piece forming with the polymer composition of comparative example 12; And
Fig. 4 is a TEM figure, shows the configuration of surface of the test piece forming with the polymer composition of comparative example 13.
Embodiment
Segmented copolymer of the present invention comprises the first block and the second block.The first block comprises epoxy group(ing), the second block without.
This first block comprises monomeric unit and this first block with epoxy group(ing) and comprises acrylic ester monomeric unit, or methacrylate ester monomeric unit, or the combination of acrylic ester monomeric unit and methacrylate ester monomeric unit; This second block comprises styrenic monomers unit, and the epoxy equivalent (weight) of this segmented copolymer is between 1,000 gram/equivalent to 20, and between 000 gram/equivalent, its molecular weight distributing index is between 1.0 to 2.0.
Preferably, the epoxy equivalent (weight) of this segmented copolymer is between 1,000 gram/equivalent to 10, between 000 gram/equivalent; More preferably, between 2,000 grams/equivalent to 10, between 000 gram/equivalent; Best, between 2,000 grams/equivalent to 6, between 000 gram/equivalent.
Preferably, the molecular weight distributing index of this segmented copolymer is between 1.0 to 1.8; More preferably, between 1.0 to 1.7; Best, between 1.0 to 1.6.
Preferably, the number molecular-weight average of this segmented copolymer is between 3,000 to 80,000; More preferably, between 5,000 to 50,000; Best, between 7,000 to 25,000.And the number molecular-weight average of the first block is between 1,000 to 55,000; More preferably, between 2,000 to 35,000; Best, between 3,000 to 15,000.When the number molecular-weight average of segmented copolymer and the number molecular-weight average of the first block are in above-mentioned scope, except thering is good compatibilized effect, use the polymer composition of this compatibility agent also to have preferably processing fluidity.
The present invention's the first block comprises the monomeric unit with epoxy group(ing), and preferably, this monomeric unit with epoxy group(ing) is unsaturated carboxylic acid Racemic glycidol ester units.More preferably, this unsaturated carboxylic acid glycidyl ester (unsaturated carboxylic acid glycidyl ester) unit is glycidyl acrylate (GA) unit, glycidyl methacrylate (GMA) unit, ethyl propylene acid glycidyl ester (glycidyl ethacrylate) unit, glycidyl itoconate (glycidylitaconate) unit etc., or the combination of described unit.
Segmented copolymer of the present invention is by this is had to monomeric unit, acrylic ester monomer and/or this methacrylate ester monomer of epoxy group(ing), and this styrenic monomers is carried out living free radical polymerization and made.
Acrylic ester monomer of the present invention,, containing epoxy group(ing), is not particularly limited in addition.Acrylic ester monomer concrete example is as methyl acrylate (methyl acrylate), ethyl propenoate (ethyl acrylate), vinylformic acid n-propyl (n-propyl acrylate), n-butyl acrylate (n-butyl acrylate), tert-butyl acrylate (t-butyl acrylate), the just own ester of vinylformic acid (n-hexyl acrylate), cyclohexyl acrylate (cyclohexyl acrylate), 2-EHA (2-ethylhexyl acrylate), lauryl acrylate (lauryl acrylate), isobornyl acrylate (isobornyl acrylate), vinylformic acid cyclododecane ester (cyclododecyl acrylate), vinylformic acid chloromethyl ester (chloromethyl acrylate), vinylformic acid 2-chloromethyl ester (2-chloroethylacrylate), vinylformic acid 2-hydroxy methacrylate (2-hydroxyethyl acrylate), vinylformic acid 3-hydroxy propyl ester (3-hydroxypropyl acrylate), vinylformic acid 2,3,4,5, the own ester of 6-penta hydroxy group (2,3,4,5,6-pentahydroxyhexyl acrylate), vinylformic acid 2,3,4,5-tetrahydroxy pentyl ester (2,3,4,5-tetrahydroxypentyl acrylate) etc.Preferably, can select methyl acrylate, ethyl propenoate, butyl acrylate etc.Present techniques can be used one or more above-mentioned monomer.
Methacrylate ester monomer of the present invention,, containing epoxy group(ing), is not particularly limited in addition.Methacrylate ester monomer concrete example is as methyl methacrylate (methyl methacrylate, hereinafter to be referred as MMA), β-dimethyl-aminoethylmethacrylate (ethyl methacrylate), n propyl methacrylate (n-propyl methacrylate), n-BMA (n-butyl methacrylate), Tert-butyl Methacrylate (t-butylmethacrylate), the just own ester of methacrylic acid (n-hexyl methacrylate), cyclohexyl methacrylate (cyclohexyl methacrylate), 2-Ethylhexyl Methacrylate (2-ethylhexyl methacrylate), lauryl methacrylate(LMA) (laurylmethacrylate), isobornyl methacrylate (isobornyl methacrylate), methacrylic acid cyclododecane ester (cyclododecyl methacrylate), methacrylic acid chloromethyl ester (chloromethyl methacrylate), methacrylic acid 2-chloromethyl ester (2-chloroethyl methacrylate), 2-hydroxyethyl methacrylate (2-hydroxyethyl methacrylate), methacrylic acid 3-hydroxy propyl ester (3-hydroxypropyl methacrylate), methacrylic acid 2,3,4,5, the own ester of 6-penta hydroxy group (2,3,4,5,6-pentahydroxyhexyl methacrylate), methacrylic acid 2,3,4,5-tetrahydroxy pentyl ester (2,3,4,5-tetrahydroxypentyl methacrylate) etc.Preferably, can select methyl methacrylate, β-dimethyl-aminoethylmethacrylate, n-BMA etc.Present techniques can be used one or more above-mentioned monomer.
While needing, the first block also can comprise other monomeric unit, for example vinylbenzene (styrene), alpha-methyl styrene (α-methylstyrene), between vinyl toluene (m-methylstyrene), o-methyl styrene (o-methylstyrene), p-methylstyrene (p-methylstyrene), adjacent ethyl styrene (o-ethylstyrene), to ethyl styrene (p-ethylstyrene), p-tert-butylstyrene (p-t-butylstyrene), vinyl cyanide (acrylonitrile), methacrylonitrile (methacrylonitrile), ethyl acrylonitrile (ethacrylonitrile), vinyl-acetic ester (vinylacetate), N-methyl maleimide (N-methyl maleimide), N-ethylomaleimide (N-ethyl maleimide), N-cyclohexyl maleimide (N-cyclohexylmaleimide), N-phenyl maleimide (N-phenyl maleimide), acrylimide (acrylamide), methacrylic imide (methacrylamide), N-methacrylic imide (N-methyl acrylamide), butoxymethyl acrylimide (butoxymethyl acrylamide), N-propyl methyl imide (N-propylmethacrylamide).The present invention can use one or more above-mentioned monomer.For having asked preferably compatibilized effect, acrylic ester monomeric unit in the first block and the total amount of methacrylate ester monomeric unit, in the gross weight of the first block, above for better to account for 30 % by weight, more than being more preferred from 50 % by weight, the best is more than 80%.
Styrenic monomers of the present invention, is not particularly limited.Styrenic monomers concrete example is as vinylbenzene (styrene), alpha-methyl styrene (α-methylstyrene), 4-vinyl toluene (4-methylstyrene), 2-methyl styrene (2-methylstyrene), 3-vinyl toluene (3-methylstyrene), 4-methoxy styrene (4-methoxystyrene), p-t-butyl styrene (p-t-butylstyrene), p-n-butylbenzene ethene (p-n-butylstyrene), p-tertiary butyl methoxy styrene (p-tert-butylmethoxystyrene), 2-hydroxymethyl vinylbenzene (2-hydroxymethylstyrene), 2-chloro-styrene (2-chlorostyrene), 4-chloro-styrene (4-chlorostyrene), 2, 4-dichlorostyrene (2, 4-dichlorostyrene) etc.Preferably, can select vinylbenzene, alpha-methyl styrene.
In addition, depending on the circumstances or the needs of the situation, the second block, except styrenic monomers unit, also can comprise other monomeric unit, for example vinyl cyanide (acrylonitrile), methacrylonitrile (methacrylonitrile), ethyl acrylonitrile (ethacrylonitrile), methyl acrylate, methyl methacrylate, vinyl-acetic ester (vinylacetate), N-methyl maleimide (N-methyl maleimide), N-ethylomaleimide (N-ethyl maleimide), N-cyclohexyl maleimide (N-cyclohexylmaleimide), N-phenyl maleimide (N-phenyl maleimide), acrylimide (acrylamide), methacrylic imide (methacrylamide), N-methacrylic imide (N-methyl acrylamide), butoxymethyl acrylimide (butoxymethyl acrylamide), N-propyl methyl imide (N-propylmethacrylamide) etc.Preferably, can select vinyl cyanide, methyl methacrylate.The present invention can use one or more above-mentioned monomer.For having asked preferably compatibilized effect, above-mentioned comprise other monomeric unit in the situation that, the styrenic monomers unit in the second block, in the gross weight of the second block, above for better to account for 30 % by weight, more than being more preferred from 50 % by weight, the best is more than 80%.
Segmented copolymer of the present invention obtains by living free radical polymerization, wherein living free radical polymerization can be general existing nitrogen oxygen [free radical] regulation and control polymerizations (Nitroxide-Me diated Polymerization), Transfer Radical Polymerization (Atom transfer Radical Polymerization), reversible addition-fracture chain transfer method (Reversible Addition-Fragmentation Chain Transfer), organic tellurium living radical polymerization (organotellurium-me diated living radicalpolymerization), reversible chain transfer catalysis polymerization (Reversible chain transfer catalyzed polymerization).
Preferably, preparation is during segmented copolymer of the present invention, uses containing tellurium compound and azo based compound as polymerization starter.
Should be to be selected from suc as formula the organic telluride shown in (1), suc as formula two tellurides shown in (2) containing tellurium compound, or a combination of described telluride.
What the application's specific embodiment was used is suc as formula the organic telluride shown in (1) and suc as formula two tellurides shown in (2) containing tellurium compound.
(R
7Te)
2(2)
In formula (1), R
1for C
1to C
8alkyl, aryl, substituted aryl or aromatic heterocyclic radical; R
2and R
3for hydrogen atom or the C of respectively doing for oneself
1to C
8alkyl, and R
4for aryl, substituted aryl, aromatic heterocyclic radical, acyl group, oxygen base carbonyl or cyano group.
R
1shown in particularly as described below:
C
1to C
8the concrete example of alkyl can be as the alkyl of the straight chain shape of the carbonatomss 1 to 8 such as methyl, ethyl, n-propyl, sec.-propyl, cyclopropyl, normal-butyl, sec-butyl, the tertiary butyl, cyclobutyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, a chain or ring-type.Desirable alkyl is straight chain shape or the branched-chain alkyl of carbonatoms 1 to 4, more preferably methyl, ethyl or normal-butyl.
The concrete example of aryl can be as phenyl, naphthyl etc.The concrete example of substituted aryl can be to have substituent phenyl, have substituent naphthyl etc.The concrete example of fragrant heterocyclic radical can be pyridyl, pyrryl, furyl, thienyl etc.Substituting group in above-mentioned substituted aryl can be halogen atom, hydroxyl, alkoxyl group, amido, nitro, cyano group, contains-COR
5shown carbonyl (R
5=C
1to C
8alkyl, aryl, C
1to C
8alkoxyl group, aryloxy), alkylsulfonyl, trifluoromethyl etc.Desirable R
1for phenyl, trifluoromethyl substituted-phenyl.Again, above-mentioned substituting group better, with 1 or 2 replacements, is better positioned at contraposition or ortho position.
R
2and R
3shown each base is particularly as described below:
C
1to C
8the concrete example of alkyl can be and above-mentioned R
1the base that shown alkyl is identical.
R
4shown base is particularly as described below:
The concrete example of aryl, substituted aryl, aromatic heterocyclic radical can be and above-mentioned R
1the base that shown base is identical.
The concrete example of acyl group can be formyl radical, ethanoyl, benzyl acyl group etc.
Oxygen base carbonyl preferably-COOR
6(R
6=hydrogen atom, C
1to C
8alkyl, aryl) shown in base, concrete example is as carboxyl, methoxycarbonyl, ethoxy carbonyl, propoxycarbonyl, n-butoxy carbonyl, sec-butoxy carbonyl, tert-butoxycarbonyl, n-pentyloxy carbonyl, phenyloxycarbonyl etc.Desirable preferably methoxycarbonyl, ethoxy carbonyl of oxygen base carbonyl.
Desirable R
4preferably aryl, substituted aryl, oxygen base carbonyl or cyano group.Aryl is phenyl preferably.Substituted aryl is halogen atom substituted-phenyl, trifluoromethyl substituted-phenyl preferably.When again, described substituting group is halogen atom better with 1 to 5 replacement.During for alkoxyl group or trifluoromethyl better with 1 or 2 replacements, contraposition or ortho position more fortunately while replacing with 1, while replacing with 2 more fortunately between position.Preferably methoxycarbonyl, ethoxy carbonyl of oxygen base carbonyl.
Organic telluride shown in desirable formula (1) is with R
1for C
1to C
4alkyl, R
2and R
3for hydrogen atom or C
1to C
4alkyl, R
4for the compound shown in aryl, substituted aryl, oxygen base carbonyl better.Better R
1for C
1to C
4alkyl, R
2and R
3for hydrogen atom or C
1to C
4alkyl, R
4for phenyl, substituted-phenyl, methoxycarbonyl, ethoxy carbonyl.
Organic telluride shown in formula (1) is particularly as described below:
The concrete example of organic telluride is as (methyl tellurium-methyl) benzene, (1-methyl tellurium-ethyl) benzene, (2-methyl tellurium-propyl group) benzene, the chloro-4-of 1-(1-methyl tellurium-ethyl) benzene, 1-trifluoromethyl-4-(1-methyl tellurium-ethyl) benzene, 2-methyl tellurium-2 Methylpropionic acid methyl esters, 2-methyl tellurium-2 Methylpropionic acid ethyl ester, [Ethyl-2-Methyl-2-methyl tellurium-propionic ester], 2-(normal-butyl tellurium)-2 Methylpropionic acid ethyl ester, [Ethyl-2-Methyl-2-normal-butyl tellurium-propionic ester], 1-(1-methyl tellurium-ethyl)-3,5-pair-trifluoromethylbenzene, the fluoro-6-of 1,2,3,4,5-five (1-methyl tellurium-ethyl) benzene, 2-methyl tellurium propionitrile, 2-methyl-2 methyl tellurium propionitrile, (ethyl tellurium-methyl) benzene, (1-ethyl tellurium-ethyl) benzene, (2-ethyl tellurium-propyl group) benzene, 2-ethyl tellurium-2 Methylpropionic acid methyl esters, 2-ethyl tellurium-2 Methylpropionic acid ethyl ester, 2-ethyl tellurium propionitrile, 2-methyl-2-ethyl tellurium propionitrile, (normal-butyl tellurium-methyl) benzene, (1-normal-butyl tellurium-ethyl) benzene, (2-normal-butyl tellurium-propyl group) benzene, 2-normal-butyl tellurium-2 Methylpropionic acid methyl esters, 2-normal-butyl tellurium-2 Methylpropionic acid ethyl ester, 2-normal-butyl tellurium propionitrile, 2-methyl-2-normal-butyl tellurium propionitrile etc.
In formula (2), R
7with the R in above-mentioned formula (1)
1definition identical.
Two tellurides shown in desirable formula (2) are with R
7for C
1to C
4alkyl or phenyl better.
Compound shown in formula (2) can be particularly dimethyl two tellurides, diethyl two tellurides, two-n-propyl, two tellurides, di-isopropyl two tellurides, two cyclopropyl two tellurides, di-n-butyl two tellurides, two-sec-butyl, two tellurides, two-tertiary butyl, two tellurides, two cyclobutyl two tellurides, phenylbenzene two tellurides, two-(p-p-methoxy-phenyl) two tellurides, two-(p-aminocarbonyl phenyl) two tellurides, two-(p-nitrophenyl) two tellurides, two-(p-cyano-phenyl) two tellurides, two-(p-alkylsulfonyl phenyl) two tellurides, dinaphthyl two tellurides, bipyridyl two tellurides etc.Preferably dimethyl two tellurides, diethyl two tellurides, two-n-propyl, two tellurides, di-n-butyl two tellurides, phenylbenzene two tellurides.More preferably dimethyl two tellurides, diethyl two tellurides, two-n-propyl, two tellurides, di-n-butyl two tellurides.
In addition, in the present invention, in order to promote polymerization velocity, can add azo based compound as polymerization starter.The azo based compound using, as long as the azo based compound that radical polymerization is used conventionally, is not particularly limited.Concrete example is as 2,2 '-azo two-isopropyl cyanide (AIBN), 2,2 '-azo two-2-methylbutyronitrile (AMBN), 2,2 '-azo two-2,4-methyl pentane nitrile (ADVN), 1,1 '-azo two-1-cyclohexanenitrile (ACHN), dimethyl-2,2 '-azo-bis-iso-butyl (MAIB), 4,4 '-azo two-4-cyanopentanoic acid (ACVA), 1,1 '-azo two-(1-acetoxyl group-1-diphenylphosphino ethane), 2,2 '-azo two (2 methylbutyryl amine), 2,2 '-azo two (4-methoxyl group-2,4-methyl pentane nitrile), 2,2 '-azo two (2,2,4-dimethylpentane), 2-itrile group-2-propyl group azoformamide, 2,2 '-azo two (2,2,4-dimethyl amidino groups propane) diacid salt, 2,2 '-azo two [2-(2-tetrahydroglyoxaline-2-yl) propane ", 2,2 '-azo two [2-methyl-N-(2-hydroxyethyl) propionic acid amide], 2,2 '-azo two (2,4,4-trimethylpentane), 2,2 '-azo two (N-butyl-2-methyl propanamide), 2,2 '-azo two (N-cyclohexyl-2-methyl propanamide) etc.
Above-mentioned these azo based compounds, if better according to the suitable selection of reaction conditions.For example in low temperature polymerization (below 40 ℃) situation with 2,2 '-azo two-2,4-methyl pentane nitrile (ADVN), 2,2 '-azo two (4-methoxyl group-2,4-methyl pentane nitrile), middle temperature polymerization (40～80 ℃) situation is with 2,2 '-azo two-isopropyl cyanide (AIBN), 2,2`-azo, two-2-methylbutyronitrile (AMBN), dimethyl-2,2 '-azo-bis-iso-butyl (MAIB), 1,1 '-azo two-(1-acetoxyl group-1-diphenylphosphino ethane) is applicable to using 1,1 '-azo two-1-cyclohexanenitrile (ACHN) in high temperature polymerization, 2-itrile group-2-propyl group azoformamide, 2,2 '-azo two (N-butyl-2-methyl propanamide), 2,2 '-azo two (N-cyclohexyl-2-methyl propanamide), 2,2 '-azo two (2,4,4-trimethylpentane), while being used aqueous solvent, to use 4,4 '-azo two-4-cyanopentanoic acid (ACVA) in reaction, 2,2 '-azo two (2 methylbutyryl amine), 2,2 '-azo two (2,2,4-dimethyl amidino groups propane) diacid salt, 2,2 '-azo two [2-(2-tetrahydroglyoxaline-2-yl) propane], 2,2 '-azo two [2-methyl-N-(2-hydroxyethyl) propionic acid amide] is good.
About the Organic Tellurium Compounds shown in formula (1) and the usage quantity of azo based compound, conventionally for 1 mole of the Organic Tellurium Compounds shown in formula (1), the usage quantity of azo based compound is 0.01 mole to 100 moles, preferably 0.05 mole to 100 moles, more preferably 0.1 mole to 10 moles, be preferably 0.1 mole to 5 moles.
Polymerization can be carried out under solvent-free, also can use general the used organic solvent of radical polymerization.Spendable solvent is benzene, toluene, DMF (DMF), dimethyl sulfoxide (DMSO) (DMSO), acetone, chloroform, tetracol phenixin, tetrahydrofuran (THF) (THF), ethyl acetate, trifluoromethylbenzene etc. such as.Again, also can use aqueous solvent, such as water, methyl alcohol, ethanol, Virahol, propyl carbinol, ethanol cellosolve (Ethylcellosolve), ethylene glycol butyl ether (Butyl cellosolve), 1-methoxy-2-propanol etc.The usage quantity of solvent is as long as suitably regulate.For 1 g of vinyl-type monomer, solvent is 0.01 milliliter-100 milliliters, preferably 0.01 milliliter-10 milliliters, and more preferably 0.1 milliliter-1 milliliter.
Then, above-mentioned mixture is stirred.Temperature of reaction, reaction times, as long as do suitably to regulate according to the molecular weight of obtained living-radical polymers or molecular weight distributing index, stir 1 minute to 100 hours at 0 ℃ to 150 ℃ conventionally.More fortunately 20 ℃ to 100 ℃ are stirred 0.1 hour to 48 hours.Better at 20 ℃ to 80 ℃, stir 0.1 hour to 24 hours.So, even also can high-level efficiency obtain accurate molecular weight distribution (PDI) in oligomerization temperature and short polymerization time.Now, pressure carries out conventionally under normal pressure, also can under pressurization or decompression, carry out.
After having reacted, by ordinary method, under reduced pressure remove and use solvent or residual monomer, take out purpose polymers the insoluble solvent of application target polymkeric substance, by redeposition, process object is emanated.Redeposition is processed as long as do not exert an influence for object itself, can use any known treatment process.
The molecular weight of segmented copolymer of the present invention can be adjusted according to the amount of reaction times and Organic Tellurium Compounds, wherein, and to obtain number molecular-weight average as 3,000～80,000 polymkeric substance is good, and number molecular-weight average is 5,000～50,000 multipolymer is better.
After polyreaction completes, in the remaining tellurium atom of molecular end, can be by tributyl tin or containing radical reduction methods such as the compounds of Sulfur, activated carbon, silica gel, active aluminum, atlapulgite, the adsorption method such as molecular sieve and polymeric sorbent, the method of the adsorbing metal of ion exchange resin etc., add the superoxide of aqueous hydrogen peroxide solution or benzoyl peroxide etc., send into the gases such as air or oxygen simultaneously, make the tellurium atom of multipolymer end be oxidized and decompose, by making water or appropriate solvent, remove the liquid-liquid extraction method of residual tellurium atom or leaching method etc., or the combination of above method also can.
Polymer composition of the present invention comprises following component: styrenic, non-styrenic and segmented copolymer as above.
Preferably, this styrenic concrete example is as poly styrene polymer, impact polystyrene polymkeric substance (HIPS), SAN (AS), styrene-acrylonitrile-butadiene polymkeric substance (ABS), methyl methacrylate-styrene-butadiene polymkeric substance (MBS), Methyl Methacrylate-Styrene-acrylonitrile-butadiene copolymers (MABS), Methyl Methacrylate-Styrene polymkeric substance (MS), styrene-butadiene block copolymer, styrene-ethylene-butadiene-styrene block copolymer (SEBS), styrene isoprene segmented copolymer, styrene-ethylene-propylene-based block copolymer (SEPS), or these combination.
Preferably, this non-styrenic concrete example if with polymkeric substance, methacrylate ester polymkeric substance, the acrylic ester polymer of epoxy reaction, or these combination.
Wherein can be with the polymkeric substance of epoxy reaction for containing hydroxyl (OH), acidic group (COOH), amido (NH
2), acid anhydrides (acid anhydride), amide group (CONH
2) etc. functional group's polymkeric substance.
Preferably, this can be with the polymkeric substance concrete example of epoxy reaction as polylactic acid polymer, starch polymer (starch polymer), polycarbonate (PC), polymeric amide (PA), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), thermoplastic polyurethane (TPU), or the combination of described polymkeric substance.
The concrete example of polylactic acid polymer has L-type poly(lactic acid) (PLLA), D type poly(lactic acid), D, L-type poly(lactic acid) (PDLLA) etc.
Polycarbonate concrete example has dihydroxyphenyl propane (2, two (4-hydroxy phenyl) propane of 2-), dihydroxyphenyl propane (two (4-hydroxy phenyl) methane), dihydroxyphenyl propane (4,4 '-dihydroxybiphenyl), dihydroxyphenyl propane (1, two (4-hydroxy phenyl) ethane of 1-), dihydroxyphenyl propane (two (3-methyl-4-hydroxy phenyl) propane of 2,2-).Reactive for asking polycarbonate and epoxy group(ing) to have preferably, the hydroxyl of polycarbonate end is above for better to account for 2 % by mole of whole ends, is more preferred from more than 10 % by mole.
The concrete example of polymeric amide has nylon 6, nylon 66, nylon 11, nylon 12, NYLON610, nylon 46 etc.
Preferably, the multipolymer that this methacrylate ester polymkeric substance is polymethylmethacrylate or methyl methacrylate and methyl acrylate.
Preferably, this acrylic ester polymer is polymethyl acrylate.
The polymeric constituent of above-described polymer composition there is no particular restriction method for making, can be the polymerization of generally knowing and comprises overall polymerization, solution polymerization process, overall-suspension polymerization, suspension polymerization etc.
Between the component of polymer composition of the present invention, there is no particular restriction for content, visual required mechanical properties is suitably selected the content of every kind of component, but wherein segmented copolymer must meet epoxy equivalent (weight) between 1,000 gram/equivalent to 20, between 000 gram/equivalent, its molecular weight distributing index is between 1.0 to 2.0.And the acrylic ester monomeric unit in the first block and/or the total amount of methacrylate ester monomeric unit, in the gross weight of the first block, above for better to account for 30 % by weight, more than being more preferred from 50 % by weight, the best is more than 80%.Styrenic monomers unit in the second block, in the gross weight of the second block, above for better to account for 30 % by weight, more than being more preferred from 50 % by weight, the best is more than 80%.
Wherein, better, the better and optimum range of the epoxy equivalent (weight) of this segmented copolymer and molecular weight distributing index is as aforementioned, so repeat no more.If when the epoxy equivalent (weight) of segmented copolymer exceedes 20,000 grams/equivalent, the improvement effect of compatibility agent cannot be brought into play, and causes polymer-compatible poor effect; If when the epoxy equivalent (weight) of segmented copolymer is less than 1,000 gram/equivalent, there is the doubt that causes crosslinked phenomenon thereby cause polymer strength to weaken, and use too much during containing epoxy compounds, also can cause the situation of the wasting of resources to occur.In addition,, if molecular weight distributing index is greater than at 2 o'clock, consistency poor effect, cannot reach effect required for the present invention.
In addition, the better and better form of the number molecular-weight average of this segmented copolymer and the number molecular-weight average of the first block is also as aforementioned, so also repeat no more.
Preferably, in order to prepare at least one component in this polymer composition, by use, contain tellurium compound and make as polymerization starter.
More preferably, this segmented copolymer contains tellurium compound by use and makes as polymerization starter.
In addition,, in this polymer composition, the weight ratio of styrene polymer and non-styrene polymer is between 2 to 98 to 98 to 2.Preferably, weight ratio is between 5 to 95 to 95 to 5.More preferably, weight ratio is between 15 to 75 to 75 to 15.
In addition,, in this polymer composition, when this styrenic and this non-styrenic add up to 100 weight part, the segmented copolymer content adding is between 0.1 to 30 weight part.Preferably, when this styrenic and this non-styrenic add up to 100 weight part, the segmented copolymer content adding is between 0.2 to 20 weight part.More preferably, when this styrenic and this non-styrenic add up to 100 weight part, the segmented copolymer content adding is between 0.5 to 15 weight part.
Polymer composition of the present invention is by being obtained by mixing this styrenic, this non-styrenic and this segmented copolymer.If necessary, also can further contain other additive, for example lubricant (as Zinc Stearate, calcium stearate or ethene-bis-stearic acid amides), plasticizer (as Dormant oils), antioxidant (as the antioxidant of phenol or phosphorus system), UV light absorber, fire retardant chemical, static inhibitor, filler, tinting material, and diformazan silicone oil, as long as these additives can not become the important factor that affects effect of the present invention.
The moulded product of polymer composition of the present invention, can make by any mechanography.For example injection molding, extrusion molded and extrude molded.Can utilize extrusion molded sheet material, film or the tubing of obtaining, for example, utilize extrusion die and the expandable die of T-mould (unstretched, uniaxial extension or biaxial stretch-formed).
In the application's specific embodiment, contriver uses a forcing machine that said components is mixed, and the design temperature of this forcing machine is according to general technology, depending on needing the kind of the polymkeric substance mixing different and different.
Embodiment
The present invention will be described further with regard to following examples, but will be appreciated that, described embodiment is only for illustrating use, and should not be interpreted as restriction of the invention process.
The number molecular-weight average (Mn) of following multipolymer and molecular weight distributing index (PDI=MW/Mn) are to utilize gel permeation chromatography (GPC) to try to achieve, its instrument using is a liquid chromatograph (factory plate model is Shimadzu L C-10, and tubing string is wherein that Shodex K-804L+K805L, polystyrene standards are TOSOH TSK standard substance).
Epoxy equivalent (weight) is to be calculated and obtained by the formula shown in following formula (p), and oxirane value (epoxy group(ing) mole number/100 gram polymkeric substance) is wherein to record by following steps: first, make in acetic acid and toluene Mixed Solvent that polymer dissolution is 1: 1 in proportioning, add again tetrabutyl bromine ethamine, be mixed with the solution that tetrabutyl bromine ethamine concentration is 0.2M, then by 0.1M HClO
4carry out potentiometric titration.
Epoxy equivalent (weight)=100/ oxirane value (p)
[preparing segmented copolymer]
< embodiment 1>
The operation steps of the present embodiment is as follows:
(1) metallic tellurium of 6.38g (50mmol) [Aldrich system, trade(brand)name: Tellurium (40 sieve aperture)] is suspended in the THF of 50ml, and at room temperature n-Butyl Lithium (Aldrich system, 1.6M hexane solution) 34.4ml (55mmol) is low dripped (10 minutes), and this reaction soln is stirred, until metallic tellurium completely dissolve lasts 20 minutes.In this reaction soln, under room temperature, add (1-bromotrifluoromethane) benzene 11.0g (60mmol), stir 2 hours.After question response finishes, under decompression, solvent is concentrated, then implement underpressure distillation, obtain the BuTe-(CH (CH that presents yellow oil
3) Ph) 8.66g (productive rate 70%).
(2) under nitrogen state, the BuTe-(CH (CH that the Diisopropyl azodicarboxylate of 0.1g (AIBN), 0.5g step (1) are made
3) Ph), 0.05g (Ph-Te)
2the toluene of MMA, the 20.0g of GMA, the 19.0g of (Acros system, trade(brand)name: Diphenyl ditelluride), 1.0g is placed in 100ml reaction flask and carries out polyreaction, and setting temperature of reaction is 60 ℃; Reaction times is 7 hours, and to obtain a prepolymer, its transformation efficiency can reach 100%, and the number molecular-weight average (Mn) that records this prepolymer through sampling is 19,424; Molecular weight distributing index (PDI) is 1.46.
(3) by the toluene of the styrene monomer of the prepolymer of step (1), 40g (SM) and 40.0g, at 60 ℃, carry out polyreaction for the second time, last 24 hours.
(4) add the toluene of 40.0g, and temperature of reaction is promoted to 95 ℃, then react 24 hours, and then make a segmented copolymer of the present invention.
(5) after question response finishes, add the normal hexane of 1000g that this segmented copolymer is separated out, then, in general purifying mode, filter and dry this segmented copolymer, its turnover ratio is about 65%, and record its Mn through sampling, is 30,651; PDI is 1.64; Epoxy equivalent (weight) is 5,096.
< embodiment 2 is to 10>
Embodiment 2 to 10 prepares segmented copolymer of the present invention with the step identical with embodiment 1, reaction times in step (1) in embodiment 4 changed into 24 hours, the place that other embodiment is different is only: kind and the consumption of the reactant that wherein used are not quite similar, aforesaid operations parameter is as shown in table 1 below, and the epoxy equivalent (weight) of product and molecular weight distributing index are as shown in table 3 below.
Table 1
Note 1:[-] not interpolation of representative.
Note 2:AN represents vinyl cyanide.
< comparative example 1 is to 4>
Comparative example 1 to 4 is to prepare segmented copolymer with the step identical with embodiment 1, the place of main difference is: kind and the consumption of the reactant that wherein used are not quite similar, these operating parameterss are as shown in table 2 below, and the epoxy equivalent (weight) of product and molecular weight distribution are as shown in table 3 below.In addition, also need supplementary notes, the reaction times in the step (2) of comparative example 1 and comparative example 2 changes 24 hours into; And the reaction times again of the step of comparative example 3 (4) changes 72 hours into.
Table 2
Note: [-] representative is not added.
< comparative example 5>
The operation steps of this comparative example is as follows: prior to the reaction flask that under nitrogen state, the toluene of the MMA of the GMA of the SM of the AIBN of 0.2g, 20g, 1.0g, 19.0g, 20.0g is placed in to 100ml, carry out polyreaction, setting temperature of reaction is 60 ℃, reaction times is 36 hours, and then add the toluene of 20g, and temperature of reaction is promoted to 95 ℃, react again 36 hours, and then make a multipolymer, special instruction, the segment being formed by monomers such as SM, GMA and MMA in this multipolymer is that random (random) arranges.
After reaction finishes, add the normal hexane of 1000g that this multipolymer is separated out, then, in general purifying mode, filter and dry this multipolymer, its transformation efficiency is about 92%, and record its Mn through sampling, is 21,909, and PDI is 2.38, epoxy equivalent (weight) is 5,076, and these data also arrange in following table 3.
Table 3
Note: the weight part of the component in table is respectively that gross weight take this first block and the second block is as 100 parts.
< comparative example 6 is to 8>
The multipolymer of comparative example 6 to 8 is all commercial goods, is respectively sequentially synthetic made AFUF ON UG-4040 (unregulated polymer of vinylbenzene and epoxy compounds, the M in East Asia
w=11,000,476 grams/equivalent of epoxy equivalent (weight)), synthetic made AFUFON UG-4070 (unregulated polymer of vinylbenzene and epoxy compounds, the M in East Asia
w=9,700,714 grams/equivalent of epoxy equivalent (weight)), and the made JONCRYL ADR-4368 (unregulated polymer) of Johnson Polymer.
[preparing polymer composition]
< embodiment 11>
The present embodiment is first to use a forcing machine (model is EX-100) (label is for strange beautiful by the high impact polystyrene of 1.5kg (HIPS); Model is PH-55Y), (label is Nature Works for the PLA of 1.5kg; Model is 3001D), and the segmented copolymer of 150g embodiment 1 extrudes at 190 ℃, lasts after 10 minutes, then with a biaxial extruder extruding pelletization, can obtain a polymer composition.
Above-mentioned polymer composition penetrates the test piece of 1/8 inch, measures the cantilever beam impact strength (impact strength) of this test piece according to ASTMD256 standard testing method, i.e. Izod value, and its test result is as shown in table 4 below.
< embodiment 12 to 24 and comparative example 9 are to 17>
Embodiment 12 to 24 is to prepare polymer composition of the present invention with the step identical with embodiment 11 with comparative example 9 to 17, different places are: kind and the consumption of the component wherein used are not quite similar, and the temperature of extruding also has difference along with the kind difference of component, and described operating parameters is as shown in table 4 below.
Similarly, after the various embodiments described above and comparative example are extruded, penetrate the test piece of 1/8 inch, according to ASTM D256 standard testing method, measure the cantilever beam impact strength of these test pieces, these test results are as shown in table 4 below.
Table 4
Note 1: the unit of the consumption of component is weight part, and this weight part is that the gross weight that adds up to take styrenic and non-styrenic is as 100 parts.
Note 2: embodiment 11 to 14,18 and 21 HIPS that use are strange U.S. made PH-55Y; The HIPS that embodiment 20 is used is strange U.S. made PH-88S.
Note 3: in above-described embodiment and comparative example, the ABS using is strange U.S. made PA-757; PBT is the beautiful made PBT-1200M in east; PC is strange U.S. made PC-110; And the PA made 2N that is platformization.
Note 4:ABS represents that acrylonitrile-butadiene-styrene terpolymer, PBT represent that polybutylene terephthalate, PC represent that polycarbonate, PA represent polymeric amide.
[form (morphology) of polymer composition]
Contriver gets respectively the polymer composition of embodiment 11, embodiment 15, comparative example 12 and comparative example 13, and these polymer compositions are made into and meet the test piece that transmission electron microscope (TEM) is observed, and with its configuration of surface of transmission electron microscope observation, and the TEM of described test piece schemes as shown in Figures 1 to 4 sequentially, its enlargement ratio is all 5000 times.
In Fig. 1, white portion is PLA; Dark grey and the part with inaccessible structure (occlusion structure) rubber particles are HIPS; As shown in Figure 1, (domain) is little for the block of HIPS, and the consistency of the each component in the polymer composition of expression embodiment 11 is good.
In Fig. 2, Fig. 3 and Fig. 4, white portion is PLA; Black and Dark grey part are AB S; Light grey part is AS (acrylonitrile-styrene copolymer).Three figure of comparison of aforementioned, obviously visible, the block of the AS in Fig. 2 is less, and the each component compatibility in the polymer composition of expression embodiment 15 is good, and the block of AS in Fig. 3 and Fig. 4 is larger, represent that the consistency of the each component in the polymer composition of comparative example 12 and 13 is not good.
In sum, present inventor is by making this acrylic ester monomer and/or this methacrylate ester monomer, and this styrenic monomers is carried out living free radical polymerization, and then make the segmented copolymer of the present invention with specified molecular weight dispersion index and epoxy equivalent (weight) scope, and further it should be used for preparing polymer composition of the present invention, by the epoxy group(ing) in this segmented copolymer, make the consistency between different types of polymeric constituent better, and then the mechanical properties of lifting polymer composition, therefore really can reach object of the present invention.
Claims (17)
1. a segmented copolymer, is characterized in that consisting of:
The first block, comprises monomeric unit and this first block with epoxy group(ing) and comprises acrylic ester monomeric unit, methacrylate ester monomeric unit, or the combination of acrylic ester monomeric unit and methacrylate ester monomeric unit; And
The second block, is comprised of styrenic monomers unit and acrylonitrile monemer unit; And the epoxy equivalent (weight) of this segmented copolymer is between 1,000 gram/equivalent to 20, and between 000 gram/equivalent, its molecular weight distributing index is between 1.0 to 2.0.
2. segmented copolymer according to claim 1, is characterized in that, take the total amount of this second block as 100 % by weight, the content of this styrenic monomers unit is 70 % by weight, and the content of this acrylonitrile monemer unit is 30 % by weight; This first block is comprised of glycidyl methacrylate unit and methyl methacrylate monomer unit, take the total amount of this first block as 100 % by weight, the content of this glycidyl methacrylate unit in this first block is 5 % by weight, and the content of this methyl methacrylate monomer unit is 95 % by weight.
3. segmented copolymer according to claim 1, is characterized in that, the molecular weight distributing index of this segmented copolymer is between 1.0 to 1.8.
4. segmented copolymer according to claim 1, is characterized in that, this monomeric unit with epoxy group(ing) is unsaturated carboxylic acid Racemic glycidol ester units.
5. segmented copolymer according to claim 4, it is characterized in that, this unsaturated carboxylic acid Racemic glycidol ester units is the combination of glycidyl acrylate unit, glycidyl methacrylate unit, ethyl propylene acid glycidyl ester unit, glycidyl itoconate unit or described unit.
6. segmented copolymer according to claim 1, is characterized in that, it contains tellurium compound by use and makes as polymerization starter.
7. a polymer composition, is characterized in that comprising following component:
Styrenic;
Non-styrenic, and
Segmented copolymer according to claim 1.
8. polymer composition according to claim 7, is characterized in that, this non-styrenic be selected from can with the polymkeric substance of epoxy reaction, methacrylate ester polymkeric substance, acrylic ester polymer, or the combination of described polymkeric substance.
9. polymer composition according to claim 7, it is characterized in that, this non-styrenic is to be selected from methyl acid methyl acrylate-methyl acrylate copolymer, poly(lactic acid), starch polymer, polycarbonate, polymeric amide, polyethylene terephthalate, polybutylene terephthalate, thermoplastic polyurethane, or the combination of described polymkeric substance.
10. polymer composition according to claim 7, is characterized in that, the epoxy equivalent (weight) of this segmented copolymer is between 1,000 gram/equivalent to 10, between 000 gram/equivalent.
11. polymer compositions according to claim 7, is characterized in that, the number molecular-weight average of this segmented copolymer is between 3,000 to 80,000; And the number molecular-weight average of this first block is between 1,000 to 55,000.
12. polymer compositions according to claim 7, is characterized in that, the molecular weight distributing index of this segmented copolymer is between 1.0 to 1.8.
13. polymer compositions according to claim 7, is characterized in that, the monomeric unit with epoxy group(ing) in this segmented copolymer is unsaturated carboxylic acid Racemic glycidol ester units.
14. polymer compositions according to claim 13, it is characterized in that, this unsaturated carboxylic acid Racemic glycidol ester units is glycidyl acrylate unit, glycidyl methacrylate unit, ethyl propylene acid glycidyl ester unit, glycidyl itoconate unit, or the combination of described unit.
15. polymer compositions according to claim 7, is characterized in that, this segmented copolymer contains tellurium compound by use and makes as polymerization starter.
16. polymer compositions according to claim 7, is characterized in that, the weight ratio of this styrenic and this non-styrenic is between 2 to 98 to 98 to 2.
17. polymer compositions according to claim 16, is characterized in that, when this styrenic and this non-styrenic add up to 100 weight part, this segmented copolymer is 0.1 to 30 weight part.
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