CN100572411C - Acrylic star polymer - Google Patents

Acrylic star polymer Download PDF

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CN100572411C
CN100572411C CNB2005800170618A CN200580017061A CN100572411C CN 100572411 C CN100572411 C CN 100572411C CN B2005800170618 A CNB2005800170618 A CN B2005800170618A CN 200580017061 A CN200580017061 A CN 200580017061A CN 100572411 C CN100572411 C CN 100572411C
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methyl
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formula
ester
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CN1957006A (en
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松本仁志
中村光宏
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Nippon Soda Co Ltd
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Nippon Soda Co Ltd
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Abstract

The object of the present invention is to provide narrow molecular weight distribution and structure Be Controlled the acrylic star polymer with sour decomposability.This star polymer is a nuclear portion to have by having 2 polymer chains with the polyacrylic ester repeat units derived of the part-structure of following formula (I) expression at least; With following polymer chain is arm, and this polymer chain is the polymer chain that has by (methyl) acrylate repeat units derived of formula (II) expression, and the R in the formula (I) 1During for methyl, this polymer chain does not comprise having by R 5Homopolymer chain for (methyl) acrylate repeat units derived of C1～C4 alkyl.In the described formula (I), R 1Expression hydrogen atom or methyl, R 2And R 3Represent the organic group with carbon atom bonding independently of one another, Cl carbon is represented the carbon atom by carbon atom and other part bondings.In the described formula (II), R 4Expression hydrogen atom or methyl, R 5The expression organic group.

Description

Acrylic star polymer
Technical field
The present invention relates to acrylic star polymer, in more detail, relate to be nuclear portion by the polyacrylic ester repeat units derived, being the star polymer of arm by the acrylate repeat units derived.
The application is willing to 2004-162081 number based on the spy who filed an application on May 31st, 2004 and the spy that filed an application on April 28th, 2005 is willing to require right of priority 2005-132073 number, and quotes its content at this.
Background technology
Knownly can obtain star-like polymkeric substance by the following method: with 1, the phenylbenzene hexyl lithium that 1-diphenylethlene and s-butyl lithium reaction obtain is an initiator, make methyl methacrylate, Propenoic acid, 2-methyl, isobutyl ester, the polymerization of methacrylic tert-butyl acrylate, then, with dicumyl alcohol dimethacrylate or 2,5-dimethyl-2, the reaction of 5-hexanediol dimethacrylate obtains star-like polymkeric substance (with reference to non-patent literature 1).
Non-patent literature 1:L.Kilian, et.al., J.Polymer Science, Part A, 2003,3083.
Summary of the invention
But the molecular weight distribution of above-claimed cpd is nearly all more than 1.5, and not talkative molecular weight is under control.In addition, utilize this point, attempt, but not necessarily obtain sufficient character used as erosion resistant with sour decomposability.
The object of the present invention is to provide narrow molecular weight distribution and structure Be Controlled the acrylic star polymer with sour decomposability.
The inventor etc. study intensively in order to solve above-mentioned problem, found that, by using the organic group that has specific skeleton in the acrylate portion that constitutes arm, and have the nuclear portion of tertiary carbon skeleton by use, can solve above-mentioned problem, thereby finish the present invention.
That is, the present invention relates to:
(1) star polymer is characterized by, and is nuclear portion to have by having 2 polymer chains with the polyacrylic ester repeat units derived of the part-structure of following formula (I) expression at least; With following polymer chain is arm, and this polymer chain is the polymer chain that has by (methyl) acrylate repeat units derived of formula (II) expression, and the R in the formula (I) 1During for methyl, this polymer chain does not comprise having by R 5Homopolymer chain for (methyl) acrylate repeat units derived of C1～C4 alkyl;
[Chemical formula 1]
(in the formula (I), R 1Expression hydrogen atom or methyl, R 2And R 3Represent the organic group with carbon atom bonding independently of one another, C1 carbon is represented the carbon atom by carbon atom and other part bondings.)
[Chemical formula 2]
Figure C20058001706100052
(in the formula (II), R 4Expression hydrogen atom or methyl, R 5The expression organic group.)
(2) as (1) described star polymer, it is characterized by, having 2 polyacrylic ester with the part-structure of following formula (I) expression is diacrylates of formula (III) expression,
[chemical formula 3]
Figure C20058001706100061
(in the formula (III), R 11And R 21Represent hydrogen atom or methyl independently of one another, R 12, R 13, R 22And R 23Represent organic group independently of one another, R by carbon atom bonding 33Expression divalent linking group.)
(3) as (2) described star polymer, it is characterized by, in the formula (III), R 33For having substituting group or not having substituent alkylidene group.
(4) star polymer is characterized by, and has at least one repeating unit that is selected from repeating unit with lactonic ring and the repeating unit with ester ring type skeleton at arm.
(5) as (4) described star polymer, it is characterized by, nuclear portion has by having 2 polyacrylic ester repeat units derived with the part-structure of following formula (I) expression at least.
[chemical formula 4]
Figure C20058001706100062
(in the formula (I), R 1Expression hydrogen atom or methyl, R 2And R 3Represent the organic group with carbon atom bonding independently of one another, C1 carbon is represented the carbon atom by carbon atom and other part bondings.)
As mentioned above, star polymer of the present invention is because narrow molecular weight distribution, sour decomposability are also excellent, so be useful in erosion resistant etc., we can say the utility value height on the industry.
Embodiment
Constitute the nuclear portion of star polymer of the present invention, it is characterized by, serving as reasons has 2 polyacrylic ester repeat units derived with the part-structure of following formula (I) expression at least.In addition, when being described as acrylate, comprise acrylate and methacrylic ester.In the formula (I), R 1Expression hydrogen atom or methyl.R 2And R 3Represent organic group independently of one another with carbon atom bonding.At this moment, said organic group represents to have at least the general name of the functional group of 1 carbon atom, and said organic group with carbon atom bonding is meant that the element of the α position of C1 carbon in the organic group is a carbon atom.Particularly, but example goes out methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, the tertiary butyl, cyclopropyl, cyclohexyl, benzyl, styroyl, phenyl, 1-naphthyl, vinyl, allyl group, ethynyl, propargyl, chloromethyl, 2-chloroethyl, 1-chloroethyl, 2-pyridyl, 2-pyridylmethyl etc.
C1 carbon removes and Sauerstoffatom, R 2And R 3In conjunction with beyond, also have an associative key, it is characterized in that bonded the other side is carbon atom.That is to say, do not combine with carbon atoms such as Sauerstoffatom, sulphur atom atom in addition.As being other terminal parts with the carbon atom,, just there is not particular restriction so long as can have the structure of the part-structure of at least one formula (I) expression.Particularly, the structure shown in can the following chemical formula 5～chemical formula 7 of example.Wherein, omitted the part-structure of formula (I) expression.In addition, the part-structure of the formula more than 2 (I) expression can be identical, also can be different.
[chemical formula 5]
Figure C20058001706100081
[chemical formula 6]
Figure C20058001706100091
[chemical formula 7]
Figure C20058001706100101
Particularly, but preferred exemplary with formula (III) expression polyacrylic ester.In the formula (III), R 11And R 21Represent hydrogen atom or methyl independently of one another, R 12, R 13, R 22And R 23Represent organic group independently of one another by carbon atom bonding, can example at R 2And R 3The same object lesson that middle example goes out.R 33Expression two ends are the divalent linking group of carbon atom, the divalent substituting group in equally can example chemical formula 5～chemical formula 7 shown substituting groups.Wherein, R 33Be preferably and have substituting group or do not have substituent alkylidene group.As the polyacrylic ester that has the part-structure of representing with formula (I) more than 2 at least, specifically example compound shown below.
[chemical formula 8]
Figure C20058001706100111
(methyl) acrylate derived polymers chain by formula (II) expression that the present invention is used is characterized by the R in the formula (I) 1During for methyl, this polymer chain does not comprise having by R 5Homopolymer chain for (methyl) acrylate repeat units derived of C1～C4 alkyl.In the formula (II), R 4Expression hydrogen atom or methyl, R 5The expression organic group.Said organic group is the general name that contains the functional group of 1 carbon atom at least, particularly, can example with at R 2And R 3In the identical group of object lesson that goes out of example, but preferred exemplary have alicyclic hydrocarbon skeleton organic group, have the organic group of lactonic ring.
As organic group with alicyclic hydrocarbon skeleton, the concrete organic group represented with following formula V of example.
[chemical formula 9]
-A-B···(V)
In the formula V, A represents singly-bound, ether, ester group, carbonyl, alkylidene group or the divalent group that their combinations are obtained, B represent in the following chemical formula (VI-1)～(V1-6) any it
[Chemical formula 1 0]
Figure C20058001706100121
In the above-mentioned chemical formula (VI-1)～(VI-6), R 111Expression C1～C5 alkyl, Z are represented to form the necessary atomic group of alicyclic hydrocarbon radical with carbon atom.R 112～R 116The C1 that maybe can have side chain～C4 alkyl or alicyclic hydrocarbon radical of representing straight chain in the hydrocarbon independently of one another, but R 112～R 114In at least one or R 115And R 116In one of any expression alicyclic hydrocarbon radical.R 117～R 121The C1 that maybe can have side chain～C4 alkyl or alicyclic hydrocarbon radical of representing hydrogen atom, straight chain independently of one another, but R 117～R 121In at least 1 the expression alicyclic hydrocarbon radical, R 119And R 121In one of any expression C1 straight chain or that have side chain～C4 alkyl or alicyclic hydrocarbon radical.R 122～R 125The C1 that maybe can have side chain～C4 alkyl or alicyclic hydrocarbon radical of representing hydrogen atom, straight chain independently of one another, but R 122～R 125In at least one the expression alicyclic hydrocarbon radical.As alicyclic hydrocarbon radical, the concrete skeleton shown in the following chemical formula of example.
[Chemical formula 1 1]
Figure C20058001706100131
Wherein, preferred 1-adamantyl, 2-adamantyl, but the 2-of the following chemical formula of preferred exemplary (VII) expression replaces adamantyl.
[Chemical formula 1 2]
Figure C20058001706100141
In the formula (VII), R 130Expression can have substituent alkyl, R 131～R 132Represent halogen atom, alkyl, cycloalkyl, alkenyl, alkoxyl group, carbalkoxy or acyl group independently of one another, p, q, r represent the arbitrary integer in 0 or 1～3 respectively independently, and p, q or r are 2 when above, R 131Between, R 132Between and R 133Between can be the same or different respectively.
As A, the concrete divalent group of the following chemical formulation of example.
[Chemical formula 1 3]
Figure C20058001706100142
In the above-mentioned chemical formula, Ra and Rb represent hydrogen atom, alkyl, substituted alkyl, halogen atom, alkoxyl group independently of one another, particularly, but low alkyl groups such as preferred exemplary methyl, ethyl, n-propyl, sec.-propyl, normal-butyl.As the substituting group of substituted alkyl, can enumerate halogen atom, alkoxyl group, as alkoxyl group, but the alkoxyl group of C1～C4 such as example methoxyl group, oxyethyl group, propoxy-, butoxy.As halogen atom, but example chlorine atom, bromine atoms, fluorine atom, iodine atom etc.R1 represents arbitrary integer of 1～10, and m represents arbitrary integer of 1～3.
In the formula (II), as R 5(methyl) acrylate of expression alicyclic hydrocarbon radical, but the compound shown in the following chemical formula of example.In addition, in the chemical formula, R 6And R 7The low alkyl group of representing straight or branched independently of one another.
[Chemical formula 1 4]
Figure C20058001706100161
[Chemical formula 1 5]
Figure C20058001706100171
[Chemical formula 1 6]
Figure C20058001706100181
[Chemical formula 1 7]
Figure C20058001706100191
As (methyl) acrylate with the organic group that contains lactonic ring, particularly, but example butyrolactone acrylate, butyrolactone methacrylic ester, mevalonolactone methacrylic ester, pantoyl lactone methacrylic ester etc., but but the organic group of the following formula of preferred exemplary (VIII) expression.
[Chemical formula 1 8]
-A-C···(VIII)
In the formula, A represents the group identical with above-mentioned divalent group, and C represents the arbitrary group in the following chemical formula (IX-1)～(IX-5).
[Chemical formula 1 9]
Figure C20058001706100201
In the chemical formula (IX-1)～(IX-5), X represents that Sauerstoffatom, sulphur atom maybe can have substituent alkylidene group, R 201Expression can have substituent alkyl, cycloalkyl or alkenyl.M1 represents arbitrary integer of 0 or 1～5, and m1 is 2 when above, R 201Between can be mutually the same also can be different, in addition, also can mutually combine forms ring.As (methyl) acrylate with lactonic ring, the specifically compound shown in the following chemical formula of example.
[Chemical formula 2 0]
Figure C20058001706100211
[Chemical formula 2 1]
Figure C20058001706100221
[Chemical formula 2 2]
[Chemical formula 2 3]
Figure C20058001706100241
[Chemical formula 2 4]
Figure C20058001706100251
The arm of star polymer of the present invention preferably constitutes: have at least one by above-mentioned (methyl) acrylate repeat units derived or be selected from least one repeating unit in the repeating unit that contains following formation.
As the repeating unit that constitutes arm, particularly, but the following repeating unit of example.
(a) have the repeating unit of lactonic ring and have the ester ring type skeleton repeating unit,
(b) have the repeating unit of lactonic ring and have the tertiary carbon skeleton repeating unit,
(c) have the repeating unit of lactonic ring and have acid decomposition/leavings group repeating unit,
(d) have the repeating unit of ester ring type skeleton and have the tertiary carbon skeleton repeating unit and
(e) repeating unit that has the repeating unit of ester ring type skeleton and have acid decomposition/leavings group.
The arm of repeating unit that contains repeating unit, the repeating unit with ester ring type skeleton with lactonic ring, has the repeating unit of tertiary carbon skeleton and have an acid decomposition/leavings group is preferably by (methyl) acrylate repeat units derived.
In addition, the arm of repeating unit that contain repeating unit, the repeating unit with ester ring type skeleton with lactonic ring, has the repeating unit of tertiary carbon skeleton and have acid a decompositions/leavings group is preferably by (methyl) acrylate repeat units derived that has lactonic ring, ester ring type skeleton, tertiary carbon skeleton and sour decomposition/leavings group in ester portion.
In addition, the arm that contains by (methyl) acrylate repeat units derived with tertiary carbon skeleton preferably has the tertiary carbon skeleton in the α position of ester oxygen, the carbon that contains by the α position of the ester oxygen of the arm of (methyl) acrylate repeat units derived that has the ester ring type skeleton in ester portion is preferably tertiary carbon, and the arm that contains the repeating unit with ester ring type skeleton is preferably by (methyl) vinylformic acid 2-alkyl-2-adamantane radical ester or the different diamantane ester of (methyl) vinylformic acid repeat units derived.
As (methyl) acrylate that has the tertiary carbon skeleton in ester portion, particularly, but example tert-butyl acrylate, methacrylic tert-butyl acrylate, vinylformic acid 1,1-dimethyl propyl ester, methacrylic acid 1,1-dimethyl ester etc.
The arm of star polymer of the present invention is except that containing by above-mentioned (methyl) acrylate repeat units derived, can also contain as required by (methyl) acrylate repeat units derived shown in following.
Methyl acrylate, ethyl propenoate, propyl acrylate, tert-butyl acrylate, the vinylformic acid pentyl ester, cyclohexyl acrylate, EHA, Octyl acrylate, vinylformic acid uncle monooctyl ester, vinylformic acid chloroethene ester, vinylformic acid 2-ethoxy ethyl ester, vinylformic acid 2,2-dimethyl-3-oxyethyl group propyl ester, vinylformic acid 5-oxyethyl group pentyl ester, vinylformic acid 1-methoxyl group ethyl ester, vinylformic acid 1-ethoxy ethyl ester, vinylformic acid 1-methoxyl group propyl ester, vinylformic acid 1-methyl isophthalic acid-methoxyl group ethyl ester, vinylformic acid 1-(isopropoxy) ethyl ester, benzyl acrylate, the vinylformic acid methoxy benzyl ester, vinylformic acid chaff ester, esters of acrylic acids such as tetrahydrofurfuryl acrylate; Methyl methacrylate, Jia Jibingxisuanyizhi, propyl methacrylate, isopropyl methacrylate, the methacrylic acid pentyl ester, the methacrylic tert-butyl acrylate, N-Hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, methacrylic acid benzyl chloride ester, Octyl methacrylate, methacrylic acid 2-ethoxy ethyl ester, methacrylic acid 4-methoxyl group butyl ester, methacrylic acid 5-methoxyl group pentyl ester, methacrylic acid 2,2-dimethyl-3-oxyethyl group propyl ester, methacrylic acid 1-methoxyl group ethyl ester, methacrylic acid 1-ethoxy ethyl ester, methacrylic acid 1-methoxyl group propyl ester, methacrylic acid 1-methyl isophthalic acid-methoxyl group ethyl ester, methacrylic acid 1-(isopropoxy) ethyl ester, methacrylic acid chaff ester, methyl acrylic esters such as tetrahydrofurfuryl methacrylate;
Methyl crotonate, ethyl crotonate, the Ba Dousuan propyl ester, the Ba Dousuan pentyl ester, the Ba Dousuan cyclohexyl, the Ba Dousuan ethylhexyl, the Ba Dousuan monooctyl ester, Ba Dousuan uncle monooctyl ester, Ba Dousuan chloroethene ester, Ba Dousuan 2-ethoxy ethyl ester, Ba Dousuan 2,2-dimethyl-3-oxyethyl group propyl ester, Ba Dousuan 5-oxyethyl group pentyl ester, Ba Dousuan 1-methoxyl group ethyl ester, Ba Dousuan 1-ethoxy ethyl ester, Ba Dousuan 1-methoxyl group propyl ester, Ba Dousuan 1-methyl isophthalic acid-methoxyl group ethyl ester, Ba Dousuan 1-(isopropoxy) ethyl ester, the crotons acid benzyl ester, the Ba Dousuan methoxy benzyl ester, Ba Dousuan chaff ester, crotonate classes such as Ba Dousuan tetrahydrochysene chaff ester; Dimethyl itaconate, diethyl itaconate, the methylene-succinic acid dipropyl, the methylene-succinic acid diamyl ester, methylene-succinic acid two cyclohexyls, methylene-succinic acid two (ethylhexyl) ester, dioctyl itaconate, methylene-succinic acid two uncle's monooctyl esters, methylene-succinic acid two (chloroethyl) ester, methylene-succinic acid two (2-ethoxyethyl group) ester, methylene-succinic acid two (2,2-dimethyl-3-ethoxycarbonyl propyl) ester, methylene-succinic acid two (5-oxyethyl group amyl group) ester, methylene-succinic acid two (1-methoxy ethyl) ester, methylene-succinic acid two (1-ethoxyethyl group) ester, methylene-succinic acid two (1-methoxy-propyl) ester, methylene-succinic acid two (1-methyl isophthalic acid-methoxy ethyl) ester, methylene-succinic acid two (1-(isopropoxy) ethyl) ester, the methylene-succinic acid dibenzyl ester, methylene-succinic acid two (methoxy-benzyl) ester, methylene-succinic acid two chaff esters, itaconic ester classes such as methylene-succinic acid two (tetrahydrofurfuryl) ester etc.
The ratio of each repeating unit in the arm of star polymer of the present invention can be selected arbitrarily according to the used monomeric ratio of reaction.For example, the content with repeating unit of lactonic ring is 30～70 moles of % of the whole repeating units of arm, is preferably 35～65 moles of %, more preferably 40～60 moles of %.Content with repeating unit of ester ring type skeleton is generally 20～75 moles of % of the whole repeating units of arm, is preferably 25～70 moles of %, more preferably 30～65 moles of %.Content with repeating unit of lactonic ring and ester ring type skeleton structure in addition is generally 0 mole of %～70 mole % of whole monomeric repeating units, is preferably 2～40 moles of %, more preferably 5～30 moles of %.
The number-average molecular weight Mn of arm is by gel permeation chromatography and be scaled polystyrene, is preferably 1,000～100,000, and more preferably 1,500～500,000, more preferably 2,000～200,000, be preferably 2,500～100,000 especially.The ratio (Mw/Mn) of weight-average molecular weight (Mw) and number-average molecular weight (Mn) is preferably 1.01～3.00, and more preferably 1.01～2.00, more preferably 1.01～1.50.
Manufacture method as star polymer of the present invention, can example (1) in the presence of anionic polymerization initiator, (methyl) acrylate etc. that will have ester ring type skeleton and lactonic ring etc. carries out anionoid polymerization, synthetic arm polymkeric substance, the method that itself and polyacrylic ester are reacted; (2) in the presence of anionic polymerization initiator, make polyacrylic ester reaction and form multi-functional nuclear portion, make itself and (methyl) acrylate etc. carry out the method for anionoid polymerization then with ester ring type skeleton and lactonic ring etc.; (3) in the presence of anionic polymerization initiator, (methyl) acrylate etc. that will have ester ring type skeleton and lactonic ring etc. carries out anionoid polymerization, synthetic arm polymkeric substance, then, make the reaction of itself and multi-functional coupling agent, and then with the method for the monomer reaction that can carry out anionoid polymerization etc.The method of above-mentioned (1), (3) is controlled reaction easily, is preferred on the controlled star polymer of manufacturing structure.
As the anionic polymerization initiator that is used for above-mentioned anionic polymerization, but example basic metal or organic alkali metal.As basic metal, but example lithium, sodium, potassium, caesium etc.As organic alkali metal, but the above-mentioned alkali-metal alkylide of example, allylate, arylide etc.Particularly, can enumerate lithium ethide, n-Butyl Lithium, s-butyl lithium, tert-butyl lithium, sodium ethyl, biphenyl lithium, naphthyl lithium, triphenyl lithium, sodium naphthalene, alpha-methyl styrene sodium two negatively charged ion, 1,1-phenylbenzene hexyl lithium, 1,1-phenylbenzene-3-methyl amyl lithium etc.
Polyreaction as the synthetic arm polymkeric substance in the method for above-mentioned (1) or (3), the arbitrary method that drips in method that can be by dripping anionic polymerization initiator in monomer (mixing) solution and the solution that is containing anionic polymerization initiator in the method for monomer (mixing) liquid is carried out, but, preferably in containing the solution of anionic polymerization initiator, drip the method for monomer (mixing) liquid from controlling the aspect of molecular weight and molecular weight distribution.The building-up reactions of this arm polymkeric substance is being carried out under-100～50 ℃, preferred-100～40 ℃ temperature under the inert gas environments such as nitrogen, argon, in organic solvent usually.
As the used organic solvent of the building-up reactions of above-mentioned arm polymkeric substance, can enumerate fat hydrocarbons such as normal hexane, normal heptane, alicyclic hydrocarbon type such as hexanaphthene, pentamethylene, aromatic hydrocarbons such as benzene, toluene, ether, tetrahydrofuran (THF) (ethers such as THF), diox, and normally used organic solvent in anionoid polymerization such as methyl-phenoxide, hexamethylphosphoramide.These organic solvents can use with independent a kind of solvent or the mixed solvent more than two kinds.Wherein, from polarity and deliquescent viewpoint, but the mixed solvent of preferred exemplary tetrahydrofuran (THF) and toluene, tetrahydrofuran (THF) and hexane, tetrahydrofuran (THF) and methylcyclohexane.
As the polymerization methods of arm polymkeric substance, can enumerate each composition distributes by statistical way in copolymer chain integral body random copolymers, part segmented copolymer, complete segmented copolymer.The addition means of employed by selecting (methyl) esters of acrylic acid can synthesize these arm polymkeric substance respectively.
With the arm polymkeric substance that so obtains is the reaction that the branched polymer chain generates star polymer, can finish back above-mentioned polyacrylic ester of further interpolation in reaction solution by arm polymkeric substance building-up reactions and carry out.This reaction is usually being carried out polyreaction under the inert gas environments such as nitrogen, argon, in organic solvent under-100 ℃～50 ℃, preferred-70 ℃～40 ℃ temperature, thereby can obtain that structure is controlled and the polymkeric substance of narrow molecular weight distribution.In addition, carry out continuously in also can be when the forming the arm polymkeric substance used solvent of the formation reaction of described star polymer, but also can add solvent and change to form or solvent is transformed into other solvents and carry out.As described solvent, can use solvent phase used in the building-up reactions with the arm polymkeric substance with solvent.
For the manufacture method of star polymer of the present invention, preferably the mol ratio [(P)/(D)] with the reactive terminal (D) of polyacrylic ester (P) and polymer chain is set at 0.1～10, and described polymer chain is by being that the anionic polymerization of polymerization starter obtains the polymerizations such as (methyl) acrylate with ester ring type skeleton and lactonic ring with the anionic polymerization initiator.The reaction of arm polymer chain and polyacrylic ester also can be adopted the arbitrary method in the method for adding the method for polyacrylic ester and adding the arm polymer chain with reactive terminal in having the arm polymer chain of reactive terminal in polyacrylic ester.
Several addition and temperature of reaction, reaction times according to polyacrylic ester of the arm of star polymer determine, but owing to the influence of the reactive difference between the vinyl that is subjected to reactive polymer end and polyacrylic ester etc., steric hindrance etc., can generate the different a plurality of star block copolymers of arm number simultaneously usually.In addition, the ratio (Mw/Mn) of weight-average molecular weight of the star polymer of generation (Mw) and number-average molecular weight (Mn) is preferably 1.00～1.50, and number-average molecular weight is preferably 3,000～300, and 000.
(3) in the method, by making reactions such as adjusted in advance arm polymer chain and polyacrylic ester, and the centronucleus (multi-functional nuclear) that formation has reactive terminal, enable to carry out the monomer and the reaction of this centronucleus of anionoid polymerization, form new arm polymer chain, by the method for such (3), can make star polymer with different types of arm polymer chain.Also can enable to carry out the reactive terminal reaction that exists in the monomer of direct polymerization and the centronucleus, but make the method for monomer reaction after making compounds such as diphenylethlene, Stilbene reaction back or adding the inorganic acid salt of basic metal such as lithium chloride or alkaline-earth metal, when making the such reactive high monomer reaction of acrylic acid derivative, can carry out polyreaction at leisure, be favourable on the structure of the star polymer integral body that control is generated sometimes.In addition, for above-mentioned reaction, also can have in the used solvent of the centronucleus of reactive terminal and carry out continuously, and can add solvent and change and form or use other solvents to substitute described solvent and carry out in formation.As described solvent, but when example and arm polymkeric substance are synthetic used solvent phase with solvent.In addition, as in the method for above-mentioned (3) with respect to the reactive terminal that exists in the centronucleus and the arm polymer chain in the method for the new arm polymer chain of introducing or above-mentioned (2), can react the polymer chain of making random copolymerization by mixing 2 kinds of monomers, can also add 2 kinds of monomers successively and make the block polymer chain.In addition, also can finish the back and introduce functional group endways by adding carbonic acid gas, epoxide etc. in reaction.
Below, illustrate in greater detail the present invention by embodiment, but scope of the present invention is not limited to embodiment.
Embodiment 1
Under nitrogen environment, the tetrahydrofuran (THF) (THF) that 331g is contained 13 mmole lithium chlorides remains on-40 ℃, under agitation add 26 mmole s-butyl lithium (SBL), drip 88g THF solution and continue reaction 30 minutes, the THF solution of described dropping contains 97 mmole 2-Methacryloyloxy-2-methyladamantanes (2MAdMA), 78 mmoles (±)-octahydro-3-oxo-4,7-methylene radical isobenzofuran-5-ylmethyl acrylate and positional isomers (±) thereof-octahydro-1-oxo-4, the mixture (TLMA) of 7-methylene radical isobenzofuran-5-ylmethyl acrylate, with 19 mmole methacrylic tert-butyl acrylates (tBMA).From reaction system, take out a small amount of reaction soln, confirm monomer completely consumed by vapor-phase chromatography (hereinafter to be referred as GC).
Then, drip 12g and contain 22 mmoles 2,5-dimethyl-2, the THF solution of 5-hexanediol dimethacrylate (MDMA), continue reaction 30 minutes again, from reaction system, take out a small amount of reaction soln, after the completely consumed of GC affirmation MDMA monomer, utilize hydrochloric THF solution that reaction is stopped, in the water that reaction stop solution input is a large amount of, polymkeric substance is separated out, after filtering, washing, carry out drying, obtain the white powder shaped polymer.Resulting polymers is dissolved among the THF again, puts into then in a large amount of methyl alcohol, polymkeric substance is separated out, after filtering, washing, drying under reduced pressure 10 hours obtains the white powder star polymer.Resulting polymers is carried out gpc analysis, and the result is: Mw=29400, Mw/Mn=1.23, area=67% of star polymer part; The Mw=4800 of arm polymer moieties, Mw/Mn=1.19, area=33% are measured by 13C-NMR, and the ratio of components of this polymkeric substance is 2MAdMA: TLMA: tBMA: MDMA=46: 31: 11: 12 (mol ratio).
Embodiment 2
Under nitrogen environment, the THF that 233g is contained 15 mmole lithium chlorides remains on-40 ℃, under agitation add 31 mmole SBL, drip 171g and contain 88 mmole 2MAdMA, 88 mmoles methacrylic acid-5-oxo-4-oxatricyclo [4.2.1.03,7] the THF solution of nonane-2-base (NLMA) and 19 mmole tBMA continues reaction 30 minutes.From reaction system, take out a small amount of reaction soln, confirm the monomer completely consumed by GC.
Then, drip the THF solution that 12g contains 22 mmole MDMA, continue reaction 30 minutes again, from reaction system, take out a small amount of reaction soln, after the completely consumed of GC affirmation MDMA monomer, utilize hydrochloric THF solution that reaction is stopped.In the water that reaction stop solution input is a large amount of, polymkeric substance is separated out, after filtering, washing, carry out drying, obtain the white powder shaped polymer.Resulting polymers is dissolved among the THF again, puts into then in a large amount of methyl alcohol, polymkeric substance is separated out, after filtering, washing, drying under reduced pressure 10 hours obtains the white powder star polymer.Resulting polymers is carried out gpc analysis, and the result is: Mw=32700, Mw/Mn=1.23, area=52% of star polymer part; The Mw=5400 of arm polymer moieties, Mw/Mn=1.20, area=48% are measured by 13C-NMR, and the ratio of components of this polymkeric substance is 2MAdMA: NLMA: tBMA: MDMA=43: 37: 9: 11 (mol ratio).
Embodiment 3
Under nitrogen environment, the THF that 341g is contained 7 mmole lithium chlorides remains on-40 ℃, under agitation adds 14 mmole SBL, drips the THF solution that 10g contains 22 mmole 2MAdMA, continues reaction 30 minutes.From reaction system, take out a small amount of reaction soln and confirm the completely consumed of 2MAdMA monomer by GC.Then, drip the THF solution that 78g contains 66 mmole 2MAdMA, 88 mmole TLMA and 19 mmole tBMA, continue reaction 30 minutes.From reaction system, take out a small amount of reaction soln, confirm the monomer completely consumed by GC.
Then, drip the THF solution that 12g contains 22 mmole MDMA, continue reaction 30 minutes again, from reaction system, take out a small amount of reaction soln, after the completely consumed of GC affirmation MDMA monomer, utilize hydrochloric THF solution that reaction is stopped.In the water that reaction stop solution input is a large amount of, polymkeric substance is separated out, after filtering, washing, carry out drying, obtain the white powder shaped polymer.Resulting polymers is dissolved among the THF again, puts into then in a large amount of methyl alcohol, polymkeric substance is separated out, after filtering, washing, drying under reduced pressure 10 hours obtains outermost shell and disposes the unitary white powder star polymer of 2MAdMA.Resulting polymers is carried out gpc analysis, and the result is: Mw=21400, Mw/Mn=1.23, area=62% of star polymer part; The Mw=3800 of arm polymer moieties, Mw/Mn=1.13, area=38% are measured by 13C-NMR, and the ratio of components of this polymkeric substance is 2MAdMA: TLMA: tBMA: MDMA=43: 37: 10: 11 (mol ratio).
Embodiment 4
Under nitrogen environment, the THF that 343g is contained 5 mmole lithium chlorides remains on-40 ℃, under agitation adds 11 mmole SBL, drips the THF solution that 10g contains 22 mmole 2MAdMA, continues reaction 30 minutes.From reaction system, take out a small amount of reaction soln, confirm the completely consumed of 2MAdMA monomer by GC.Then, drip the THF solution that 78g contains 79 mmole 2MAdMA, 74 mmole TLMA and 19 mmole tBMA, continue reaction 30 minutes.From reaction system, take out a small amount of reaction soln, confirm the monomer completely consumed by GC.
Then, drip the THF solution that 12g contains 22 mmole MDMA, continue reaction 30 minutes again, from reaction system, take out a small amount of reaction soln, after the completely consumed of GC affirmation MDMA monomer, utilize hydrochloric THF solution that reaction is stopped.In the water that reaction stop solution input is a large amount of, polymkeric substance is separated out, after filtering, washing, carry out drying, obtain the white powder shaped polymer.Resulting polymers is dissolved among the THF again, puts into then in a large amount of methyl alcohol, polymkeric substance is separated out, after filtering, washing, drying under reduced pressure 10 hours obtains outermost shell and disposes the unitary white powder star polymer of 2MAdMA.Resulting polymers is carried out gpc analysis, and the result is: Mw=25400, Mw/Mn=1.23, area=62% of star polymer part; The Mw=4400 of arm polymer moieties, Mw/Mn=1.15, area=38% are measured by 13C-NMR, and the ratio of components of this polymkeric substance is 2MAdMA: TLMA: tBMA: MDMA=48: 32: 10: 11 (mol ratio).
Embodiment 5
Under nitrogen environment, the THF that 256g is contained 7 mmole lithium chlorides remains on-40 ℃, under agitation adds 14 mmole SBL, drips the THF solution that 10g contains 22 mmole 2MAdMA, continues reaction 30 minutes.From reaction system, take out a small amount of reaction soln, confirm the completely consumed of 2MAdMA monomer by GC.Then, drip the THF solution that 151g contains 66 mmole 2MAdMA, 88 mmole NLMA and 19 mmole tBMA, continue reaction 30 minutes.From reaction system, take out a small amount of reaction soln, confirm the monomer completely consumed by GC.
Then, drip the THF solution that 12g contains 22 mmole MDMA, continue reaction 30 minutes again, from reaction system, take out a small amount of reaction soln, after the completely consumed of GC affirmation MDMA monomer, utilize hydrochloric THF solution that reaction is stopped.In the water that reaction stop solution input is a large amount of, polymkeric substance is separated out, after filtering, washing, carry out drying, obtain the white powder shaped polymer.Resulting polymers is dissolved among the THF again, puts into then in a large amount of methyl alcohol, polymkeric substance is separated out, after filtering, washing, drying under reduced pressure 10 hours obtains outermost shell and disposes the unitary white powder star polymer of 2MAdMA.Resulting polymers is carried out gpc analysis, and the result is: Mw=29900, Mw/Mn=1.26, to measure by 13C-NMR, and the ratio of components of this polymkeric substance is 2MAdMA: NLMA: tBMA: MDMA=40: 42: 8: 10 (mol ratio).
Embodiment 6
Under nitrogen environment, the THF that 315g is contained 7 mmole lithium chlorides remains on-40 ℃, under agitation adds 14 mmole SBL, drips the THF solution that 9g contains 22 mmole methacrylic acid 1-ethyl-1-cyclohexyls (ECHMA), continues reaction 30 minutes.From reaction system, take out a small amount of reaction soln, confirm the completely consumed of ECHMA monomer by GC.Then, drip the THF that 72g contains 66 mmole ECHMA, 88 mmole TLMA and 19 mmole tBMA, continue reaction 30 minutes.From reaction system, take out a small amount of reaction soln, confirm the monomer completely consumed by GC.
Then, drip the THF solution that 12g contains 22 mmole MDMA, continue reaction 30 minutes again, from reaction system, take out a small amount of reaction soln, after the completely consumed of GC affirmation MDMA monomer, utilize hydrochloric THF solution that reaction is stopped.In the water that reaction stop solution input is a large amount of, polymkeric substance is separated out, after filtering, washing, carry out drying, obtain the white powder shaped polymer.Resulting polymers is dissolved among the THF again, puts into then in a large amount of methyl alcohol, polymkeric substance is separated out, after filtering, washing, drying under reduced pressure 10 hours obtains outermost shell and disposes the unitary white powder star polymer of ECHMA.Resulting polymers is carried out gpc analysis, and the result is: Mw=24100, Mw/Mn=1.22, area=64% of star polymer part; The Mw=3600 of arm portion, Mw/Mn=1.19, area=36% are measured by 13C-NMR, and the ratio of components of this polymkeric substance is ECHMA: TLMA: tBMA: MDMA=42: 37: 10: 11 (mol ratio).
Embodiment 7
Under nitrogen environment, the THF that 315g is contained 7 mmole lithium chlorides remains on-40 ℃, under agitation add 15 mmole SBL, drip the THF solution that 9g contains 32 mmole 1-(1-methacryloxy-1-methylethyl) diamantane (IAMA), continue reaction 30 minutes.From reaction system, take out a small amount of reaction soln, confirm the completely consumed of IAMA monomer by GC.Then, drip the THF that 74g contains 53 mmole IAMA, 85 mmole TLMA and 19 mmole tBMA, continue reaction 30 minutes.From reaction system, take out a small amount of reaction soln, confirm monomer completely consumed by GC.
Then, drip the THF solution that 13g contains 24 mmole MDMA, continue reaction 30 minutes again, from reaction system, take out a small amount of reaction soln, after the completely consumed of GC affirmation MDMA monomer, utilize hydrochloric THF solution that reaction is stopped.In the water that reaction stop solution input is a large amount of, polymkeric substance is separated out, after filtering, washing, carry out drying, obtain the white powder shaped polymer.Resulting polymers is dissolved among the THF again, puts into then in a large amount of methyl alcohol, polymkeric substance is separated out, after filtering, washing, drying under reduced pressure 10 hours obtains outermost shell and disposes the unitary white powder star polymer of IAMA.Resulting polymers is carried out gpc analysis, and the result is: Mw=30000, Mw/Mn=1.27, area=52% of star polymer part; The Mw=3400 of arm portion, Mw/Mn=1.21, area=48% are measured by 13C-NMR, and the ratio of components of this polymkeric substance is IAMA: TLMA: tBMA: MDMA=40: 40: 9: 11 (mol ratio).

Claims (5)

1, star polymer is characterized by, and is nuclear portion to have by having 2 polymer chains with the polyacrylic ester repeat units derived of the part-structure of following formula (I) expression at least; With following polymer chain is arm, and this polymer chain is the polymer chain that has by (methyl) acrylate repeat units derived of formula (II) expression, and the R in the formula (I) 1During for methyl, this polymer chain does not comprise having by R 5Homopolymer chain for (methyl) acrylate repeat units derived of C1～C4 alkyl;
In the described formula (I), R 1Expression hydrogen atom or methyl, R 2And R 3Represent methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, the tertiary butyl, cyclopropyl, cyclohexyl, benzyl, styroyl, phenyl, 1-naphthyl, vinyl, allyl group, ethynyl, propargyl, chloromethyl, 2-chloroethyl, 1-chloroethyl, 2-pyridyl or 2-pyridylmethyl independently of one another, C1 carbon is represented the carbon atom by carbon atom and other part bondings
Figure C2005800170610002C2
In the described formula (II), R 4Expression hydrogen atom or methyl, R 5The expression organic group, described organic group is the organic group with lactonic ring.
2, star polymer as claimed in claim 1 is characterized by, and having 2 polyacrylic ester with the part-structure of following formula (I) expression is diacrylates of formula (III) expression,
Figure C2005800170610003C1
In the described formula (III), R 11And R 21Represent hydrogen atom or methyl independently of one another, R 12, R 13, R 22And R 23Represent methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, the tertiary butyl, cyclopropyl, cyclohexyl, benzyl, styroyl, phenyl, 1-naphthyl, vinyl, allyl group, ethynyl, propargyl, chloromethyl, 2-chloroethyl, 1-chloroethyl, 2-pyridyl or 2-pyridylmethyl independently of one another, R 33Expression divalent linking group.
3, star polymer as claimed in claim 2 is characterized by, in the formula (III), and R 33For having substituting group or not having substituent alkylidene group.
4, star polymer as claimed in claim 1 is characterized by, and described arm also contains the repeating unit with acid decomposition/leavings group.
5, star polymer as claimed in claim 1 is characterized by, and described arm also contains the repeating unit with tertiary carbon skeleton.
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