CN110325563A - Polymer composition and its manufacturing method containing modified chlorinated polyolefin - Google Patents

Polymer composition and its manufacturing method containing modified chlorinated polyolefin Download PDF

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Publication number
CN110325563A
CN110325563A CN201880013006.9A CN201880013006A CN110325563A CN 110325563 A CN110325563 A CN 110325563A CN 201880013006 A CN201880013006 A CN 201880013006A CN 110325563 A CN110325563 A CN 110325563A
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parts
compound
methyl
allyloxy
hydroxyl
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CN110325563B (en
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小畑政示
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Kansai Paint Co Ltd
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Kansai Paint Co Ltd
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    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
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    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
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    • C08G18/16—Catalysts
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    • C08G18/24—Catalysts containing metal compounds of tin
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    • C08G18/40—High-molecular-weight compounds
    • C08G18/63—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers
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Abstract

The present invention provides manufacture excellent in stability, polymer composition containing modified chlorinated polyolefin manufacturing method and the coating comprising the polymer composition for containing modified chlorinated polyolefin.Under the coexisting with allyloxy and the compound (a) of hydroxyl, make the chloridized polyolefin (b) with allyloxy and the polymerizable monomer copolymerization containing the compound (c) selected from one or more of (methyl) acrylate, (methyl) acrylic acid and styrene, obtains the polymer composition containing modified chlorinated polyolefin.

Description

Polymer composition and its manufacturing method containing modified chlorinated polyolefin
Technical field
The present invention relates to the polymer composition containing modified chlorinated polyolefin and its manufacturing method and contain the group Close the coating composition of object.
Background technique
Nowadays, plastic material is used for various industrial fields, wherein the polyolefin-based resins such as acrylic resin are that have to be permitted The material of more excellent properties, and very economical, therefore it is widely used as the substrates such as formed article, film.But due to polyolefin The polarity of substrate is low, causes the adhesion of film formed when coating poor, therefore, to the plastic basis materials such as such polyolefin into When row coating, it is intended to take into account to the adhesion of the polyolefin substrate and with the compatibilities of other resin components contain The composition of the modified chlorinated polyolefins such as acrylic acid modified chloridized polyolefin can be used as coating or priming paint.
In the past, it as the method for obtaining the composition containing such modified chlorinated polyolefin, such as discloses such as lower section Method: make the polymerism unsaturated monomer of hydroxyl and the chlorinated polyolefin hydrocarbon reaction with anhydride group and introduce polymerism unsaturated group Group, makes method of polymerism polymerization of unsaturated monomers etc. (patent document 1, patent document 2) on the polymerism unsaturated group.
But in such prior art, have the problem that there is a situation where that manufacture stability is insufficient.
In addition, in patent document 3, as the method for improving above-mentioned manufacture stability, describing following manufacturing method: That is, hydroxyl (methyl) acrylate of the chloridized polyolefin with anhydride group and alcohol is modified, it is poly- in obtained esterification chlorination In the presence of alkene, the copolymerization of polymerizable vinyl system monomer is made to obtain modified chlorinated polyolefin resin combination in organic solvent The manufacturing method of object.But in the modified chlorinated polyolefin resin composition obtained by the manufacturing method, for with hydroxyl Base has for the composition of reactive crosslinking agent, there is a situation where that curability is insufficient.In addition, in the manufacturing method In there is also the insufficient situations of manufacture stability.
Existing technical literature
Patent document
Patent document 1: Japanese Laid-Open Patent Publication 8-59757 bulletin
Patent document 2: special open 2002-309161 bulletin
Patent document 3: special open 2015-3991 bulletin
Summary of the invention
Subject to be solved by the invention
The present invention is intended to the method for providing to obtain the polymer composition containing modified chlorinated polyolefin, is manufacture stability Excellent method.In turn, in one embodiment of the present invention, it provides to obtain the combination of polymers containing modified chlorinated polyolefin The method of object, the polymer composition containing modified chlorinated polyolefin with hydroxyl there is reactive crosslinking agent to be used in combination In the case where, excellent curability composition can be obtained.
The means to solve the problem
That is, the present invention is as described below: under the coexisting with allyloxy and the compound of hydroxyl, making with allyloxy Chloridized polyolefin and the polymerizable monomers such as acrylic monomer be copolymerized, obtain the combination of polymers containing modified chlorinated polyolefin Object.
Invention effect
It was found that if the present invention under the coexisting with allyloxy and the compound of hydroxyl in this way, make with allyloxy Chloridized polyolefin and the polymerizable monomers such as acrylic monomer be copolymerized, obtain the combination of polymers containing modified chlorinated polyolefin Object manufactures excellent in stability in the case.And then find, contain modified chlorinated polyene by what manufacturing method of the present invention manufactured The polymer composition of hydrocarbon passes through and with hydroxyl there is reactive crosslinking agent to be used in combination, and can obtain excellent curability combination Object.
Specific embodiment
Hereinafter, the embodiment that the present invention will be described in detail.
[compound (a) with allyloxy and hydroxyl]
In the present invention, under the coexisting with allyloxy and the compound (a) of hydroxyl, make the chlorination with allyloxy Polyolefin (b) and contain the compound (c) selected from one or more of (methyl) acrylate, (methyl) acrylic acid and styrene Polymerizable monomer copolymerization.Compound (a) with allyloxy and hydroxyl used in the present invention has allyl in 1 molecule Oxygroup and hydroxyl, such as the compound that logical formula (I) indicates can be enumerated；
(in formula, R1And R2Each independently represent carbon number 2 or 3 can branch alkylidene, m, n each independently represent 0 ~50 real number and m and n's and indicate 1 or more real number, can be block structure or disordered structure.)
The addition reaction of allyl alcohol and lactone；Compound and the addition reaction of lactone that logical formula (I) indicates etc..Its In, the compound that above-mentioned logical formula (I) indicates be easy to get and it is preferred that.As the specific of compound included by above-mentioned logical formula (I) Example, can enumerate allyloxyethanol, ethylene glycol monoallyl ether, diglycol monotertiary allyl ether etc., for example, 2- allyloxyethanol (also known as: ethylene glycol monoallyl ether), diglycol monotertiary allyl ether, 1- allyloxy -2- propyl alcohol are (also known as: propylene glycol monoene third Base ether, dipropylene glycol mono allyl ether, polyethylene glycol mono allyl ether, polypropylene glycol mono allyl ether, polypropylene glycol (2- allyl Oxygroup ethyl) ether, allyl alcohol and ethylene oxide and the addition reaction product of propylene oxide etc..Wherein, particularly suitable to use 2- alkene Allyloxyethanol (also known as: ethylene glycol monoallyl ether), diglycol monotertiary allyl ether.Wherein, allyloxyethanol is due to industry On be easy to get and more preferred.
As the manufacturing method for the compound that logical formula (I) indicates, well known method can be used, such as can be by making ring Oxidative ethane and/or propylene oxide are reacted with allyl alcohol, or are made selected from ethylene glycol, diethylene glycol (DEG), propylene glycol, dipropylene glycol, poly- second One or more of two pure and mild polypropylene glycols are reacted with allyl chloride or allyl alcohol and are obtained.In these reactions, as needed, Alkali compounds and/or acid compound can be made to coexist, these compounds can after the completion of reaction or in and/or remove.
[chloridized polyolefin (b) with allyloxy]
Chloridized polyolefin for example can be by being used the change with allyloxy by the chloridized polyolefin (b) with allyloxy It is polymer modified to be obtained to introduce allyloxy.As the method for introducing allyloxy to chloridized polyolefin, specifically, such as can With the following method: reacting the chloridized polyolefin with acidic group with the compound with allyloxy and hydroxyl, via acidic group With the ester condensation reaction of hydroxyl, addition has the method for the compound of allyloxy and hydroxyl in chloridized polyolefin；And make Chloridized polyolefin (d) with anhydride group is reacted with the compound with allyloxy and hydroxyl, via anhydride group and hydroxyl Addition reaction, addition has the method for the compound of allyloxy and hydroxyl in chloridized polyolefin.
As the above-mentioned chloridized polyolefin with acidic group, it can be suitable for using: polyolefin maleic acid, itaconic acid etc. are had Machine it is carboxyl acid modified and introduce after acidic group the polyolefin of chlorination again or, polyolefin is subjected to chloridized polyolefin obtained from chlorination The product of acidic group is introduced with the modification of the organic carboxyl acids such as maleic acid, itaconic acid, these are modified and chlorination can pass through known formula Method carries out.In addition, can be suitable for using as the above-mentioned chloridized polyolefin (d) with anhydride group: by polyolefin maleic acid, The organic carboxyl acids such as itaconic acid anhydride modified and introduce after anhydride group the polyolefin of chlorination again or, polyolefin is subjected to chlorination Obtained from the organic carboxyl acids such as chloridized polyolefin maleic acid, itaconic acid product (d) that is anhydride modified and introducing anhydride group, These are modified and chlorination can be carried out by known method.Polyolefin as raw material is not particularly limited, such as is preferably selected 1 kind or more of homopolymerization or copolymer from the alpha-olefin of the carbon numbers 2~10 such as ethylene, propylene, 1- butylene, 1- octene and these The copolymer etc. of other polymerizable monomers such as alpha-olefin and vinyl acetate.In these polymerizations, Ziegler Natta can be used Series catalysts, metallocene series catalysts and/or radical initiator can be the polymerization of 1 step or multistep are poly- as polymerization shape form It closes, is also possible to the polymerization of reactive rubber.In order to adjust compatibility, crystallinity, hardness, liquid stability and adhesion etc., this A little polyolefin can mix and be used as raw material.As such chloridized polyolefin (d) with anhydride group, can be used for example “スーパークロン892L”、“スーパークロン892LS”、“スーパークロン822”、“スーパークロ ン822S”、“スーパークロン930”、“スーパークロン930S”、“スーパークロン842LM”、“スー パークロン851L”、“スーパークロン3228S”、“スーパークロン3221S”、“スーパークロン 2319S " (trade name, Nippon Paper society system, maleic anhydride modified chloridized polyolefin), " ハ ー De レ Application CY-9122P ", " Ha ードレンCY-9124P”、“ハードレンHM-21P”、“ハードレンCY-1321P”、“ハードレンCY- 2121P”、“ハードレンCY-2129P”、“ハードレンF-225P”、“ハードレンF-7P”、“ハードレンM- 28P ", " ハ ー De レ Application F-2P ", " ハ ー De レ Application F-6P ", " ハ ー De レ Application CY-1132 " (trade name, Japan spin society's system, Maleic anhydride modified chloridized polyolefin) etc. commercially available products.They can be solution product or solid articles.In addition, in order to adjust Compatibility, crystallinity, hardness, liquid stability and adhesion etc., the above-mentioned chloridized polyolefin (d) with anhydride group can be single respectively Solely uses or two or more is applied in combination.In addition, the rate containing chlorine of the above-mentioned chloridized polyolefin (d) with anhydride group be preferably 10~ 35 mass %.
It is explained, even if in the higher situation of rate containing chlorine of the above-mentioned chloridized polyolefin (d) with anhydride group, this hair Bright manufacturing method also has high manufacture stability.Therefore, particularly suitable in the manufacturing method of the present invention: above-mentioned tool Have the chloridized polyolefin (d) of anhydride group rate containing chlorine be 10~35 mass %, preferably 19~32 mass %, more preferably 20~ In the range of 28 mass %.It is sometimes low to adhesion of plastic basis material etc. when rate containing chlorine is greater than 35 mass %, when being less than When 10%, stability of solution is reduced sometimes, thus is undesirable.
It is poly- relative to the chlorination with anhydride group to the amount of the acid anhydrides introduced in the chloridized polyolefin (d) with anhydride group 100 mass parts of alkene (d), preferably 0.1~8 mass parts, more preferably 0.5~3 mass parts.When the amount of the acid anhydrides of introducing is less than When 0.1 mass parts, interlayer adhesion when being occasionally used for multilayer film is low, when more than 8 mass parts, sometimes to plastic basis material Attachment it is low.
When reacting the chloridized polyolefin (d) with anhydride group with the compound with allyloxy and hydroxyl, make to have There is the compound of allyloxy and hydroxyl to add in anhydride group, the chloridized polyolefin (b) with allyloxy can be obtained.Make For the compound with allyloxy and hydroxyl, above-mentioned logical formula (I), which can be used for example, indicates such with allyloxy With the compound (a) of hydroxyl.
With used in the reacting of the chloridized polyolefin (d) with anhydride group with the compound of allyloxy and hydroxyl Amount relative to 1 mole of anhydride group, preferably 0.2~300 mole of range, more preferably 0.5~150 mole of range.Tool When having the amount of the compound of allyloxy and hydroxyl less than 0.2 mole, sometimes with the combination of polymers of modified chlorinated polyolefin The curability of object is low, in addition, sometimes, part is remaining unreacted with allyloxy after copolymerization when being greater than 300 moles Excessive with the amount of the compound of hydroxyl, the stability of the polymer composition containing modified chlorinated polyolefin is low.
Chloridized polyolefin (d) with anhydride group reacts no special limit with the compound with allyloxy and hydroxyl It is fixed, it can be carried out according to the conventional method for reacting anhydride group with hydroxyl.It specifically, such as can be above-mentioned with acid anhydrides by making The chloridized polyolefin (d) of base is with the compound with allyloxy and hydroxyl in about 20~about 160 DEG C, preferably from about 60~about 120 DEG C, the methods of more preferably from about 80~about 110 DEG C of heating about 0.5~about 72 hour carries out.It, can in order to improve the degree of progress of reaction To react at high temperature, then keep at low temperature.
In addition, the catalyst for promoting reaction can be used when above-mentioned reaction.As the catalyst, such as can make With Dibutyltin oxide, dibutyl tin dilaurate, antimony oxide, zinc acetate, manganese acetate, cobalt acetate, calcium acetate, acetic acid The Lewis acidic metals compounds such as lead, butyl titanate, tetraisopropyl titanate；Tetrabutylammonium bromide, tetraphenylphosphonium chlorideDengSalt；The catalyst known per se such as the basic nitrogen compounds class such as triethylamine, triazole.
In addition, polymerization inhibitor can be used when above-mentioned reaction.As the polymerization inhibitor, di-t-butyl hydroxyl can be used for example The compounds containing phenolic hydroxyl group such as toluene, metoxyphenol；The aromatic compounds species containing carbonyl such as benzoquinones；Skeleton containing nitroso Compounds；The polymerization inhibitors known per se such as the compounds of the skeleton of oxygroup containing N-.
In addition, the chloridized polyolefin (b) with allyloxy by make to have the chloridized polyolefin (d) of anhydride group with it is above-mentioned In the case of the compound (a) with allyloxy and hydroxyl that logical formula (I) indicates occurs obtained by addition reaction, in addition to alkene It, as needed, can also be with the above-mentioned compound with allyloxy and hydroxyl of addition other than the compound (a) of propoxyl group and hydroxyl (a) hydroxy-containing compounds other than.As the hydroxy-containing compounds other than the compound (a) with allyloxy and hydroxyl, Such as alcohol can be enumerated, there is (methyl) acryloyl group and the compound of hydroxyl etc..
It as such alcohol, such as can enumerate: the alkanols such as methanol, ethyl alcohol, propyl alcohol, butanol, 2-Ethylhexyl Alcohol；Ethylene glycol The alcohols containing ether such as single-butyl ether, propylene glycol monopropyl ether, diethylene glycol monomethyl ether；The aromatic alcohols such as benzylalcohol；Diacetone alcohol Deng the alcohols containing carbonyl；Polyalcohols such as diethylene glycol (DEG), tripropylene glycol, 1,6-HD, trimethylolpropane etc..
In addition, as the above-mentioned compound with (methyl) acryloyl group and hydroxyl, such as (methyl) acrylic acid can be enumerated 2- hydroxy methacrylate, (methyl) acrylic acid 2- hydroxy propyl ester, (methyl) acrylic acid 3- hydroxy propyl ester, (methyl) acrylic acid 4- hydroxyl fourth The monoesters compound of the dihydric alcohol of (methyl) acrylic acid such as ester and carbon number 2~8；It is somebody's turn to do the dihydric alcohol of (methyl) acrylic acid and carbon number 2~8 The 6-caprolactone modifier of monoesters compound etc..
In addition, on the above-mentioned chloridized polyolefin (d) with anhydride group the above-mentioned logical formula (I) of addition indicate there is allyl oxygen The compound (a) of base and hydroxyl has the case where hydroxy-containing compounds other than the compound (a) of allyloxy and hydroxyl with this Under, it can make the chloridized polyolefin (d) with anhydride group that addition occur with the compound (a) with allyloxy and hydroxyl After reaction, then with other than the compound (a) with allyloxy and hydroxyl hydroxy-containing compounds occur addition reaction；It can also be with The compound (a) with allyloxy and hydroxyl is added in the chloridized polyolefin (d) with anhydride group and there is allyloxy Addition reaction occurs with the pre-mixed things of the hydroxy-containing compounds other than the compound (a) of hydroxyl, alternatively, can make to have There is the chloridized polyolefin (d) of anhydride group to react with the hydroxy-containing compounds other than the compound (a) with allyloxy and hydroxyl Afterwards, then with the compound (a) with allyloxy and hydroxyl addition reaction occurs.In the chloridized polyolefin (d) with anhydride group In the case that upper also addition has the hydroxy-containing compounds other than the compound (a) of allyloxy and hydroxyl, there is allyloxy With the usage amount of the hydroxy-containing compounds other than the compound (a) of hydroxyl, relative to the chloridized polyolefin (d) with anhydride group It 1 mole of anhydride group, is not particularly limited, preferably 500 moles hereinafter, more preferable 300 moles or less.When being greater than 500 moles, It is low sometimes with the stability of the polymer composition of modified chlorinated polyolefin.In addition, with allyloxy and hydroxyl In the case that hydroxy-containing compounds other than compound (a) include the compound with (methyl) acryloyl group and hydroxyl, have The usage amount of the compound of (methyl) acryloyl group and hydroxyl, the anhydride group 1 relative to the chloridized polyolefin (d) with anhydride group Mole, preferably 10 moles hereinafter, more preferably 5 moles or less.When being greater than 10 moles, system is held in copolymerization process sometimes Gelatine easily occurs.
[contain the compound (c) selected from one or more of (methyl) acrylate, (methyl) acrylic acid and styrene Polymerizable monomer]
In this specification, " (methyl) acrylic acid " refers to " acrylic or methacrylic acid ", and " (methyl) acrylate " is Refer to " acrylate or methacrylate ", " (methyl) acryloyl group " refers to " acryloyl group or methylacryloyl ", " (first Base) acrylate " refer to " acrylate or methacrylate ".(methyl) acrylate used in the present invention, does not have Have particular determination, such as can illustrate: (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) 2-EHA, (methyl) lauryl acrylate, (methyl) cyclohexyl acrylate, the different Buddhist of (methyl) acrylic acid (methyl) alkyl acrylates such as your ketone ester；(methyl) hydroxy-ethyl acrylate, (methyl) hydroxypropyl acrylate, (methyl) acrylic acid (methyl) acrylate of the hydroxyls such as hydroxy butyl ester；Two (methyl) esters of acrylic acid such as ethylene glycol two (methyl) acrylate；(first Base) (methyl) esters of acrylic acid containing allyl such as allyl acrylate；(methyl) glycidyl acrylate etc. contains ring (methyl) esters of acrylic acid of oxygroup；Phosphoric acid 2- ((methyl) acryloxy) ethyl ester, acid phosphorus oxygroup (phospoxy) polyoxy (methyl) of the phosphorous acidic groups such as ethylene glycol list (methyl) acrylate, acid phosphorus oxygroup polyoxypropylene glycol list (methyl) acrylate Acrylate etc..In addition, styrene can be substituted, in this case, the alkane such as methyl styrene, ethyl styrene can be illustrated Base substituted type phenylethylene.In order to adjust molecular weight, hardness, polarity, adhesion, solution viscosity, the solution of polymer composition Stability and compatibility etc., these polymerizable monomers can use individually or two or more are applied in combination.
[chloridized polyolefin (b) in the case where compound (a) coexists, with allyloxy polymerizeing with containing compound (c) The copolymerization of property monomer]
In the present invention, under the coexisting with allyloxy and the compound (a) of hydroxyl, make the chlorine with allyloxy Change polyolefin (b) and containing the compound selected from one or more of (methyl) acrylate, (methyl) acrylic acid and styrene (c) polymerizable monomer copolymerization, generates modified chlorinated polyolefin.Compound (a) when copolymerization, the chlorination with allyloxy are poly- Alkene (b) and contain the compound (c) selected from one or more of (methyl) acrylate, (methyl) acrylic acid and styrene The respective usage amount of polymerizable monomer on the basis of total 100 mass parts of solid component of components described above (a)~(c), is suitable for In following range.
Compound (a) with allyloxy and hydroxyl be 0.05~40 mass parts, preferably 0.1~30 mass parts, more Preferably 0.2~20 mass parts.
Chloridized polyolefin (b) with allyloxy be 1~89.95 mass parts, preferably 5~60 mass parts, more preferably For 10~35 mass parts.
Compound (c) selected from one or more of (methyl) acrylate, (methyl) acrylic acid and styrene be 10~ 98.95 mass parts, preferably 35~95 mass parts, more preferably 65~90 mass parts.
In addition, in the present invention, under the coexisting with allyloxy and the compound (a) of hydroxyl, making with allyl The chloridized polyolefin (b) of oxygroup and containing selected from one or more of (methyl) acrylate, (methyl) acrylic acid and styrene When the polymerizable monomer copolymerization of compound (c), can further addition polymerization (methyl) acrylate, (methyl) acrylic acid and styrene with Outer copolymer composition.As such other copolymer compositions, such as vinyl acetate, sad vinyl acetate, capric acid second can be enumerated Aliphatic carboxylic acids vinyl esters such as enester etc..In addition, in order to adjust the molecular weight of polymer composition, liquid stability and compatibility Deng can be one or more of selected from the chloridized polyolefin without allyloxy and chloridized polyolefin without anhydride group Coexisting under be copolymerized.
In the present invention, being total to compound (a) (hereinafter, sometimes referred to simply as " (a) ") with allyloxy and hydroxyl It leaves, makes the chloridized polyolefin (b) (hereinafter, sometimes referred to simply as " (b) ") with allyloxy and containing selected from (methyl) propylene The polymerizable monomer of the compound (c) of one or more of acid esters, (methyl) acrylic acid and styrene is (hereinafter, sometimes referred to simply as " (c) ") copolymerization when, for molecular weight, liquid stability and the compatibility etc. for adjusting polymer composition, can be used below A kind of method: being previously added (b) into reactive tank, then polymerize while (c) is added；It is previously added (b) into reactive tank, Then it polymerize while (b) and (c) is added；It is added into reactive tank (b) and (c), then polymerize together；It is pre- into reactive tank It is first added (b) and (c), then polymerize while (b) is added；It is previously added (b) and (c) into reactive tank, then adds on one side Enter the polymerizable monomer containing compound (c) to polymerize on one side；It is previously added (b) and (c) into reactive tank, is then added on one side (b) it polymerize on one side with (c)；It polymerize while (b) and (c) is added into reactive tank；It is previously added (c) into reactive tank, so It polymerize while (b) is added afterwards；It is previously added (c) into reactive tank, is then polymerize while (b) and (c) is added；Deng. Furthermore it is possible to which polymerization process is divided into the multistage, these methods are applied in combination.For example, can be applied in combination: the 1st stage to Be added the process polymerizeing together after (b) and (c), 2 stage of He in reactive tank is added (b) and/or (c) into reactive tank on one side The process polymerizeing on one side；It or can be applied in combination: polymerize while (b) and (c) is added into reactive tank in the 1st stage The process polymerizeing while process, 2 stage of He are on one side the addition (b) into reactive tank and/or (c).In addition, by polymerization process It is divided into multistage situation, (b) used in each process and/or respective composition (c) can be identical or different.
In addition, will have the chloridized polyolefin (d) of anhydride group to mix with the compound (a) with allyloxy and hydroxyl And in the case where addition reaction occurs to obtain the chloridized polyolefin (b) with allyloxy, it is anti-by not completing above-mentioned addition It answers or the molal quantity of the compound (a) with allyloxy and hydroxyl of mixing is made to be greater than the molal quantity of anhydride group, can obtain It is mixed to the chloridized polyolefin (b) with allyloxy with what the unreacted compound (a) with allyloxy and hydroxyl coexisted Close object.It in this case, can be with alkene by being copolymerized the mixture with the polymerizable monomer containing compound (c) Under the coexisting of the compound (a) of propoxyl group and hydroxyl, make that there is the chloridized polyolefin (b) of allyloxy and contain selected from (methyl) The polymerizable monomer of the compound (c) of one or more of acrylate, (methyl) acrylic acid and styrene is copolymerized.In addition, making When chloridized polyolefin (b) with allyloxy is copolymerized with the polymerizable monomer containing compound (c), have by being pre-mixed It the chloridized polyolefin (b) of allyloxy and compound (a) with allyloxy and hydroxyl or is pre-mixed containing compound (c) polymerizable monomer and the compound (a) with allyloxy and hydroxyl, so as to allyloxy and hydroxyl Under the coexisting of compound (a), make that there is the chloridized polyolefin (b) of allyloxy and contain selected from (methyl) acrylate, (first Base) one or more of acrylic acid and styrene compound (c) polymerizable monomer copolymerization.
In the present invention, make as under the coexisting with allyloxy and the compound (a) of hydroxyl with allyloxy Chloridized polyolefin (b) with contain the chemical combination selected from one or more of (methyl) acrylate, (methyl) acrylic acid and styrene The method of the polymerizable monomer copolymerization of object (c), is not particularly limited, copolymerization process known per se can be used, wherein can fit Preferably using the solution polymerization process being polymerize in the presence of polymerization initiator in organic solvent.
As the organic solvent used in above-mentioned solution polymerization process, such as toluene, dimethylbenzene, " ス ワ ゾ ー can be enumerated The aromatics series solvents such as Le 1000 " (U ス モ petroleum society system, trade name, high point petroleum series solvent)；Hexamethylene, hexahydrotoluene Etc. alicyclic ring families solvent；The aliphatic series series solvent such as hexane, heptane；Ethyl acetate, butyl acetate, acetic acid 3- methoxybutyl, propionic acid The ester series solvents such as butyl ester, 3- ethoxyl ethyl propionate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether；First The ketone series solvents such as ethyl ketone, methyl iso-butyl ketone (MIBK), methyl amyl ketone；Butanol, 2-Ethylhexyl Alcohol, ethylene glycol monobutyl ether, dipropyl two Alcohol series solvents such as alcohol monomethyl ether etc..They can be mixed with two or more.
The usage amount of above-mentioned organic solvent when polymerization reaction is not particularly limited, and can be suitable for adjusting to adjust containing modification The stability etc. of the polymer composition of chloridized polyolefin.In addition, from the viewpoint of improving manufacture efficiency, components described above It (a) is usually suitably 500 below the mass preferably 50~400 matter on the basis of total 100 mass parts of solid component of~(c) Part is measured, in the range of more preferably 100~300 mass parts.
In addition, above-mentioned organic solvent can be added after above-mentioned copolyreaction.Alternatively, it is also possible to laggard in the copolyreaction Row desolventizing.
In addition, known compound can be used as above-mentioned polymerization initiator, for example, can enumerate methyl ethyl ketone peroxide, The peroxidating ketone such as diacetone peroxide；Two (tert-hexyl peroxide) hexamethylenes, two (tert-butyl hydroperoxide) hexamethylenes waited Oxygen ketal class；To hydroperoxide kinds such as terpane hydrogen peroxide；Di-t-butyl peroxide, two (2- t-butylperoxyisopropyls) The dialkyls class such as benzene, dicumyl peroxide；Diisobutyryl peroxide base, (the 3,5,5- trimethyl acetyl of peroxidating two Base), the peroxidating two acyls class such as dilauroyl peroxide；Dicetyl peroxydicarbonate two (2- ethylhexyl) ester, dicetyl peroxydicarbonate two The peroxy dicarbonates such as isopropyl ester, two (4- tert-butylcyclohexyl) peroxy dicarbonates；Isopropyl peroxide carbonic acid uncle The peroxycarbonates classes such as butyl ester, tert-butyl hydroperoxide carbonic acid -2- ethylhexyl；Tert-Butyl peroxypivalate, the peroxidating moon The cinnamic acid tert-butyl ester, the peroxidating 2 ethyl hexanoic acid tert-butyl ester, peroxide acetic acid butyl ester, peroxidized t-butyl perbenzoate, 2,5- bis- The peroxides esters such as methyl -2,5- two (2- ethyihexanoylperoxy) hexane, peroxidating hexahydro terephthalic acid di tert butyl carbonate；Azo is double Isobutyronitrile, azo bis- (2,4- methyl pentane nitriles), azo bis- (2- methyl propionitrile), azo bis- (2- methylbutyronitriles), 4,4'- azo Bis- (4- cyanopentanoic acids), bis- (2 Methylpropionic acid) dimethyl esters of azo, azo bis- [2- methyl-N- (2- hydroxyethyl)-propionamides], The azo compounds species such as azo bis- { 2- methyl-N- [2- (1- hydroxybutyl)]-propionamides }；Potassium peroxydisulfate, ammonium persulfate, over cure Persulfuric acid salt such as sour sodium etc..According to the free radical of generation, polymerization initiator can be simple function type or multifunctional type.
These polymerization initiators can use individually or two or more is applied in combination.Furthermore it is possible to draw in above-mentioned polymerization It sends out in agent as needed and with such as reducing agents such as sugar, sodium sulfoxylate formaldehyde, iron complex as redox initiator.
On the basis of total 100 mass parts of solid component of components described above (a)~(c), the use of above-mentioned polymerization initiator Amount is suitably usually 0.1~10 mass parts, preferably 0.5~8 mass parts, in the range of more preferably 1~6 mass parts.Pass through Change the usage amount of polymerization initiator, thus it is possible to vary the molecular weight of the polymer composition containing modified chlorinated polyolefin.In order to It is easy to manufacture with about 10,000~about 1,000,000 weight average molecular weight, improves the stability of solution and phase of polymer composition Capacitive etc., molecular weight are preferably from about 30,000~about 400,000, even more preferably about 70,000~about 200,000.
It is explained, in this specification, weight average molecular weight is when will use the reservation of gel permeation chromatograph (GPC) measurement Between (retention capacity) pass through the retention time of standard polystyren known to the molecular weight that measures under the same conditions and (retain and hold Amount) it is converted into the molecular weight of polystyrene and the value that acquires.Specifically, it can be measured: be seeped as gel under the following conditions Saturating chromatogram arrangement uses " HLC-8120GPC " (trade name, Tosoh corporation), as chromatographic column, uses " TSKgel G4000HXL ", " TSKgel G3000HXL ", " TSKgel G2500HXL " and " TSKgel G2000HXL " (trade name, For Tosoh corporation) totally 4, as detector, using differential refractometer, mobile phase: measuring temperature: tetrahydrofuran 40 DEG C, flows Speed: 1mL/ minutes.
The adding method of the polymerization initiator is not particularly limited, can be according to the suitable selection such as its type and amount.For example, It can contain in monomer mixture or solvent in advance, or can add or instill together in polymerization.
In addition, above-mentioned copolyreaction usually can 20~170 DEG C, preferably 70~130 DEG C, it is 80~120 DEG C more preferable It is carried out in range.
Furthermore it is possible to add antioxidant after above-mentioned copolyreaction.As the antioxidant, two uncles can be used for example The compounds containing phenolic hydroxyl group such as butylated hydroxytoluene, metoxyphenol；The aromatic compounds species containing carbonyl such as benzoquinones.
[polymer composition containing modified chlorinated polyolefin]
In the polymer composition of the invention containing modified chlorinated polyolefin, it can according to need containing crosslinking agent. As crosslinking agent, as long as can be combined with the above-mentioned polymer composition containing modified chlorinated polyolefin and curability group is made Close object, so that it may use arbitrary crosslinking agent, but usually be suitable for using can be with the hydroxyl that contains in above-mentioned modified chlorinated polyolefin etc. Base has reactive crosslinking agent.There is reactive crosslinking agent with hydroxyl as such, such as can be suitable for using polyisocyanate cyanogen Ester compound, blocked polyisocyanates compound, amino resins etc..Crosslinking agent can be used individually or is applied in combination Two or more.
Above-mentioned polyisocyanate compound is the compound in 1 molecule at least two isocyanate group, such as can be enumerated Aliphatic polyisocyanate, alicyclic polyisocyanates, aromatic aliphatic polyisocyanates, aromatic polyisocyanate, the polyisocyanic acid The derivative etc. of ester.
As above-mentioned aliphatic polyisocyanate, such as trimethylene diisocyanate, tetramethylene diisocyanate can be enumerated Ester, hexamethylene diisocyanate, pentamethylene diisocyanate, the third diisocyanate of 1,2-, 1,2- fourth diisocyanate, 2, 3- fourth diisocyanate, 1,3- fourth diisocyanate, 2,4,4- or 2,2,4- trimethyl hexamethylene diisocyanate, dimeric dibasic acid Diisocyanate, 2,6- diisocyanate root close aliphatic vulcabonds such as methyl caproate (common names: lysine diisocyanate)； 2,6- diisocyanate root closes caproic acid 2- isocyanato ethyl, 1,6- diisocyanate base -3- isocyanatomethyl hexane, 1,4, Tri- isocyanato- octane of 8-, tri- isocyanato- hendecane of 1,6,11-, 1,8- diisocyanate base -4- isocyanatomethyl Octane, tri- isocyanato- hexane of 1,3,6-, 2,5,7- trimethyl -1,8- diisocyanate base -5- isocyanatomethyl octane Equal aliphatic triisocyanates etc..
As above-mentioned alicyclic polyisocyanates, such as 1,3- cyclopentene diisocyanate, Isosorbide-5-Nitrae-hexamethylene two can be enumerated Isocyanates, 1,3- cyclohexane diisocyanate, 3- isocyanatomethyl -3,5,5- trimethylcyclohexylisocyanate are (logical With name: isophorone diisocyanate), 4- methyl-1,3- cyclohexene diisocyanate (common name: hydrogenation TDI), 2- methyl- 1,3- cyclohexene diisocyanate, 1,3- or bis- (isocyanatomethyl) hexamethylene (common names: hydrogenated xylylene two of 1,4- Isocyanates) or mixtures thereof, di-2-ethylhexylphosphine oxide (4,1- hexamethylene diyl) diisocyanate (common name: hydrogenation MDI), norborneol The alicyclic diisocyanates such as alkane diisocyanate；Tri- isocyanatocyclohexane of 1,3,5-, 1,3,5- trimethyl isocyano Trimethylcyclohexane, 2- (3- isocyanatopropyl) -2,5- two (isocyanatomethyl)-bicyclic (2.2.1) heptane, (3- is different by 2- Cyanate radical closes propyl) -2,6- two (isocyanatomethyl)-bicyclic (2.2.1) heptane, 3- (3- isocyanatopropyl) -2, 5- bis- (isocyanatomethyl)-bicyclic (2.2.1) heptane, 5- (2- isocyanatoethyl) -2- isocyanatomethyl -3- (3- isocyanatopropyl)-bicyclic (2.2.1) heptane, 6- (2- isocyanatoethyl) -2- isocyanatomethyl -3- (3- isocyanatopropyl)-bicyclic (2.2.1) heptane, 5- (2- isocyanatoethyl) -2- isocyanatomethyl -2- (3- isocyanatopropyl)-bicyclic (2.2.1)-heptane, 6- (2- isocyanatoethyl) -2- isocyanatomethyl -2- Alicyclic triisocyanates such as (3- isocyanatopropyl)-bicyclic (2.2.1) heptane etc..
As above-mentioned aromatic aliphatic polyisocyanates, such as di-2-ethylhexylphosphine oxide (4,1- phenylene) diisocyanate can be enumerated Or mixtures thereof (common name: MDI), 1,3- or 1,4- xylylene diisocyanate, ω, ω '-diisocyanate base -1,4- two Ethylo benzene, 1,3- or bis- (1- isocyanate group -1- Methylethyl) benzene (common name: tetramethyl xylylene diisocyanate) of 1,4- Or mixtures thereof equal aromatic aliphatics diisocyanate；The aromatic aliphatics triisocyanates such as tri- isocyanatomethylbenzene of 1,3,5- Deng.
As above-mentioned aromatic polyisocyanate, such as m-benzene diisocyanate, paraphenylene diisocyanate, 4 can be enumerated, 4 '- Diphenyl diisocyanate, 1,5- naphthalene diisocyanate, 2,4 toluene diisocyanate (common name: 2,4-TDI) or 2,6- first Or mixtures thereof phenylene diisocyanate (common name: 2,6-TDI), 4,4 '-toluidine diisocyanates, 4,4 '-diphenyl ethers two The aromatic diisocyanates such as isocyanates；Triphenyl methane -4,4 ', 4 "-triisocyanates, tri- isocyanato- benzene of 1,3,5-, The three aromatic isocyanates such as tri- isocyanato- toluene of 2,4,6-；4,4 '-diphenyl methanes -2,2 ', 5,5 '-tetraisocyanates etc. Aromatics tetraisocyanate etc..
In addition, the derivative as above-mentioned polyisocyanates, such as the two of above-mentioned polyisocyanate compound can be enumerated Polymers, trimer, biuret, allophanate, urea diketone, uretonimine (uretoimine), chlorinated isocyanurates,Diazine Triketone (oxadiazinetrione), poly methylene poly phenyl poly isocyanate (thick MDI, polymeric MDI), thick TDI etc..
Above-mentioned polyisocyanates and its derivative can be used individually or be used in combination of two or more.In addition, in these polyisocyanates In cyanate, preferred aliphatic series diisocyanate, alicyclic diisocyanate and their derivative.
In addition, as above-mentioned polyisocyanate compound, can be used makes above-mentioned polyisocyanates and its derivative and can Prepolymer obtained by the compound reacted with the polyisocyanates reacts under the conditions of isocyanate group is excessive.As can be with this The compound of polyisocyanates reaction, such as the compound with hydroxyl, amino isoreactivity hydrogen-based can be enumerated, specifically, such as Polyalcohol, low molecular weight polyester resin, amine, water etc. can be used.
In addition, the polymerism unsaturated monomer containing isocyanate group can be used as above-mentioned polyisocyanate compound Polymer or the polymerism unsaturated monomer for containing isocyanate group contain the polymerism unsaturated monomer of isocyanate group with this The copolymer of polymerism unsaturated monomer in addition.
It is different in the polyisocyanate compound from the viewpoint of curability etc. for polyisocyanate compound The equivalent proportion of the hydroxyl in resin component in cyanic acid ester group and the above-mentioned polymer composition containing modified chlorinated polyolefin (NCO/OH) it is preferably generally 0.5~2.5, the ratio of particularly preferably 0.8~1.9 range.
Above-mentioned blocked polyisocyanates compound is to block the isocyanate group of above-mentioned polyisocyanate compound The compound of agent sealing end.
As above-mentioned end-capping reagent, such as phenol, cresols, xylenol, nitrophenol, ethyl -phenol, hydroxyl hexichol can be enumerated The phenol systems such as base, butylphenol, isopropyl-phenol, nonyl phenol, octyl phenol, methyl hydroxybenzoate；Epsilon-caprolactams, δ-penta The lactams such as lactams, butyrolactam, azetidinone system；The aliphatic series such as methanol, ethyl alcohol, propyl alcohol, butanol, amylalcohol, laruyl alcohol Alcohol system；Ethylene glycol single methyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl The ethers systems such as ether, propylene glycol monomethyl ether, methoxyl group methanol；Benzylalcohol, glycolic, methyl glycollate, ethyl glycolate, glycolic fourth Ester, lactic acid, methyl lactate, ethyl lactate, butyl lactate, methylolurea, melamine methylol, diacetone alcohol, acrylic acid 2- The alcohol such as hydroxy methacrylate, 2-hydroxyethyl methacrylate system；Formyl amidoxime, acetyl amidoxime, acetoxime, methyl ethyl ketoxime, diacetyl The oximes systems such as base monoxime, diphenyl-ketoxime, hexamethylene oxime；Dimethyl malenate, diethyl malonate, malonic acid ethyl methyl esters, third The diester malonate system of the active methylene positions such as diacid two (2- methoxyl group -1- Methylethyl), ethyl acetoacetate, acetyl The series of compounds of the acetyl-containing of the active methylene position such as methyl acetate, acetylacetone,2,4-pentanedione；Butanethiol, tert-butyl mercaptan, oneself The mercaptan such as mercaptan, tert-dodecylmercaotan, 2-mercaptobenzothiazole, benzenethiol, methylbenzene phenyl-sulfhydrate, ethyl thiophenol system；Acetyl Aniline, p-methoxyacetanilide, acetyl toluidine, acrylamide, Methacrylamide, acetamide, stearmide, benzamide Equal amides system；The imide series such as succinimide, phthalimide, maleimide；Diphenylamines, nonox, diformazan The amine systems such as aniline, N- phenyl dimethylaniline, carbazole, aniline, naphthylamines, butylamine, dibutyl amine, butylaniline；Imidazoles, 2- ethyl imidazol(e) Equal imidazoles system；The ureas such as urea, thiocarbamide, ethylidene-urea, ethylene thiourea, diphenyl urea system；The amino such as N- phenylcarbamic acid phenyl ester Formic acid esters system；The imines such as aziridine, propyleneimine system；The sulphite such as sodium hydrogensulfite, potassium bisulfite system；Azoles system chemical combination Object etc..As above-mentioned azole compounds, pyrazoles, 3,5- dimethyl pyrazole, 3- methylpyrazole, 4- benzyl -3,5- diformazan can be enumerated Pyrazoles or the pyrroles such as base pyrazoles, 4- nitro -3,5- dimethyl pyrazole, the bromo- 3,5- dimethyl pyrazole of 4-, 3- methyl -5- Phenylpyrazole Zole derivatives；Imidazoles or the imdazole derivatives such as imidazoles, benzimidazole, 2-methylimidazole, 2- ethyl imidazol(e), 2- phenylimidazole；2- Imidazolidine derivatives such as methylimidazole quinoline, 2- benzylimidazoline etc..
Wherein, as preferred end-capping reagent, the diester malonate system of oxime system end-capping reagent, active methylene position can be enumerated Or series of compounds end-capping reagent, pyrazoles or the pyrazole derivatives of acetyl-containing.
When carrying out sealing end (making blocking agent reaction), addition solvent can according to need to carry out.As for blocking The solvent for changing reaction is suitably not have reactive solvent to isocyanate group, such as can enumerate as acetone, methyl ethyl ketone Esters as ketone, ethyl acetate, solvent as n-methyl-2-pyrrolidone (NMP).
As crosslinking agent, the feelings of polyisocyanate compound and/or blocked polyisocyanates compound are stated in use Under condition, as catalyst, the catalyst of common urethane reaction can be used.As the catalyst, such as can lift Tin octoate, dibutyltin diacetate, two (2 ethyl hexanoic acid) dibutyl tins, dibutyl tin dilaurate, oxalic acid dioctyl out Tin, two (2 ethyl hexanoic acid) dioctyl tins, Dibutyltin oxide, sulfurous acid dibutyl tin, dioctyl tin oxide, dibutyl tin rouge It is fat hydrochlorate, 2 ethyl hexanoic acid lead, zinc octoate, zinc naphthenate, fatty acid zinc class, Bismuth Octoate, 2 ethyl hexanoic acid bismuth, oleo-bi, new Capric acid bismuth, tertiary carboxylic acid bismuth, bismuth naphthenate, cobalt naphthenate, calcium octoate, copper naphthenate, metatitanic acid four (2- ethylhexyl) ester etc. are organic Metallic compound；Tertiary amine etc., they can use individually or two or more is applied in combination.
In addition, using catalyst, as catalytic amount, relative to above-mentioned polymer composition solid at Point total amount, in the range of preferably 0.0001~1 mass %, particularly preferably 0.0005~0.5 mass %.
In the case where above-mentioned polymer composition contains above-mentioned catalyst, from the viewpoint of storage stability, curability etc. Consider, which can contain following substance: acetic acid, propionic acid, butyric acid, isovaleric acid, caproic acid, 2 Ethylbutanoic acid, ring Alkanoic acid, octanoic acid, n-nonanoic acid, capric acid, 2 ethyl hexanoic acid, isooctyl acid, isononanoic acid, lauric acid, palmitinic acid, stearic acid, oleic acid, sub- oil Acid, neodecanoic acid, tertiary carboxylic acid, isobutyric anhydride, itaconic anhydride, acetic anhydride, citraconic anhydride, propionic andydride, maleic anhydride, butyric anhydride, lemon The organic acids such as lemon acid anhydrides, trimellitic anhydride, pyromellitic dianhydride, phthalic anhydride；The inorganic acids such as hydrochloric acid, phosphoric acid；Acetylacetone,2,4-pentanedione, Coordinating compound of the metals such as imidazole compound etc..
As above-mentioned amino resins, it is methylolated that part obtained from being reacted as amino component with aldehyde ingredient can be used Amino resins or completely methylolated amino resins.As amino component, for example, can enumerate melamine, urea, benzoguanamine, Acetylguanamine, three-dimensional guanamines (steroguanamine), loop coil guanamines (spiroguanamine), dicyandiamide etc..As aldehyde at Point, formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde etc. can be enumerated.
Further, it is possible to use the methylol of above-mentioned methylolated amino resins is carried out partially or completely with alcohol appropriate The amino resins of etherificate.As the alcohol for etherificate, such as methanol, ethyl alcohol, normal propyl alcohol, isopropanol, n-butanol, isobutyl can be enumerated Alcohol, 2- ethyl butanol, 2-Ethylhexyl Alcohol etc..
As amino resins, preferably melamine resin.As melamine resin, can be used for example will partly or completely The alkyl etherified melamine that the methylol of complete methylolated melamine resin is partially or completely etherified with above-mentioned alcohol Resin.
It as the melamine resin of abovementioned alkyl etherificate, such as can be suitable for using: will be partially or completely methylolated The methyl etherified melamine resin that the methylol of melamine resin is partially or completely etherified with methanol；Will part or The melamine for the butyl etherificate that the methylol of complete methylolated melamine resin is partially or completely etherified with butanol Polyimide resin；The methylol methanol of partially or completely methylolated melamine resin and butanol are subjected to partially or completely ether The complex etherified melamine resin etc. of the methyl-butvl of change.
As melamine resin, commercially available product can be used.As the trade name of commercially available product, such as " サ イ メ can be enumerated ル202”、“サイメル203”、“サイメル238”、“サイメル251”、“サイメル303”、“サイメル323”、 “サイメル324”、“サイメル325”、“サイメル327”、“サイメル350”、“サイメル385”、“サイメ Le 1156 ", " サ イ メ Le 1158 ", " サ イ メ Le 1116 ", " サ イ メ Le 1130 " (more than, society, オ Le ネ Network ス Japan System), " ユ ー バ Application 120 ", " ユ ー バ Application 20HS ", " ユ ー バ Application 20SE60 ", " ユ ー バ Application 2021 ", " ユ ー バ Application 2028 ", " ユ ー バ Application 28-60 " (more than, Mitsui Chemicals society system) etc..
Above-described melamine resin can use individually or two or more is applied in combination.
In addition, using melamine resin, p-methyl benzenesulfonic acid, dodecane can be used as crosslinking agent The sulfonic acid such as base benzene sulfonic acid, dinonylnaphthalene sulfonic acid；Phosphoric acid mono-n-butylester, dibutylphosphoric acid ester, list (2- ethylhexyl) phosphate, two (2- Ethylhexyl) alkyl phosphates such as phosphate；These acid and the salt of amine compounds etc. are used as catalyst.
Under the coexisting with allyloxy and the compound (a) of hydroxyl, make the chloridized polyolefin (b) with allyloxy With the polymerism list containing the compound (c) selected from one or more of (methyl) acrylate, (methyl) acrylic acid and styrene Obtained from the body copolymerization, polymer composition of the invention containing modified chlorinated polyolefin can be suitable as curability combination Object, coating composition.The polymer composition of the invention for containing modified chlorinated polyolefin is being used to combine as coating In the case where object, preferably comprising above-mentioned and hydroxyl has reactive crosslinking agent.In addition, the coating composition can according to need Cooperate the coating resins, various face such as epoxy resin, acrylic resin, polyester resin, carbamate resins, chloridized polyolefin Various additives used in the paint fields such as material, viscosity modifier, pigment dispersing agent, defoaming agent, ultraviolet absorbing agent etc..
Various known coating methods can be used to be coated in coating composition of the invention.In addition, coating object does not have There is particular determination, such as is applicable to the plastic basis materials such as formed article, film.
Embodiment
Hereinafter, enumerating Production Example, embodiment and comparative example, the present invention is further illustrated.But the present invention is not limited to This.In each example, " part " and " % " unless otherwise specified, on the basis of quality.In addition, the film thickness of film is applied based on solidification The film thickness of film.
The manufacture of polymer composition containing modified chlorinated polyolefin
Embodiment 1
" ス ー パ ー Network ロ Application 822S is packed into the four-necked bottle with cooling tube " (trade name, Nippon Paper society system, horse Come anhydride modified chloridized polyolefin, rate containing chlorine 24.5%) 100 parts, 221 parts of toluene, di-tert-butyl hydroxy toluene (abbreviation: BHT it) 0.05 part, is stirred while being blown into air into liquid phase, is warming up to about 95 DEG C, solution is made.2- alkene is added thereto 57.5 parts and 0.1 part of tetrabutylammonium bromide of allyloxyethanol, continue while reacting 2- allyloxyethanol with anhydride group Stirring.In the infrared absorptiometric analysis of solid component in the solution, in about 1770cm-1Absorbance and about 1460cm-1Extinction In the stage of ratio substantially constantization of degree, about 90 DEG C are cooled to, obtained containing the compound (a) with allyloxy and hydroxyl i.e. The solution that the concentration of about 55 parts of 2- allyloxyethanol and the chloridized polyolefin (b) with allyloxy is about 27%.Then, Stop being blown into air into liquid phase, exists about 90 DEG C while flowing into nitrogen into gas phase and continue to stir, as selected from (methyl) The compound (c) of one or more of acrylate, (methyl) acrylic acid and styrene, with about 4 hours instillation methyl methacrylates 197 parts of ester, 189 parts of cyclohexyl methacrylate, 10 parts of styrene, 2 parts of acrylic acid, 2 parts of ethylene glycol dimethacrylate, with And 5 parts of (effective components 3.5 of Perbutyl PV (trade name, You society system, 70% hydrocarbon solution of tert-Butyl peroxypivalate) Part), 189.5 parts of toluene, 63 parts of butyl acetate mixed liquor, then with about 1 hour instillation 5 parts of (effective component of Perbutyl PV 3.5 parts), 70 parts of toluene of mixed liquor, continue stir about 1 hour, then cool to room temperature, obtain containing modified chlorinated polyolefin Polymer composition (P-1).The solid component of the obtained polymer composition (P-1) containing modified chlorinated polyolefin is about 46%, about 45 parts of 2- allyloxyethanol is contained in composition.The hydroxyl value of resin solid content is about 11mgKOH/g.In addition, Chlorinated polyolefin hydrocarbon skeleton in composition is copolymerized obtained acrylic resin skeleton with by a part of 2- allyloxyethanol Ingredient ratio is about 20/80.
Embodiment 2
" ス ー パ ー Network ロ Application 822S is packed into the four-necked bottle with cooling tube " (trade name, Nippon Paper society system, horse Come anhydride modified chloridized polyolefin, rate containing chlorine 24.5%) 100 parts, 70 parts of toluene, di-tert-butyl hydroxy toluene (abbreviation: BHT) It 0.05 part, is stirred while being blown into air into liquid phase, is warming up to about 95 DEG C, solution is made.2- allyl oxygen is added thereto 23 parts and 0.1 part of tetrabutylammonium bromide of base ethyl alcohol, continue to stir while reacting 2- allyloxyethanol with anhydride group.? In the infrared absorptiometric analysis of solid component in solution, in about 1770cm-1Absorbance and about 1460cm-1Absorbance ratio The stage of substantially constantization is cooled to about 90 DEG C, is further added 150 parts and 34.5 parts of 2- allyloxyethanol of toluene, by This obtains containing about 55 parts of 2- allyloxyethanol of the compound (a) i.e. with allyloxy and hydroxyl and has allyloxy Chloridized polyolefin (b) concentration be about 27% solution.Then, stop being blown into air into liquid phase, be flowed on one side into gas phase Enter nitrogen to continue to stir at about 90 DEG C on one side, as a kind in (methyl) acrylate, (methyl) acrylic acid and styrene Above compound (c), with about 4 hours 197 parts of methyl methacrylates of instillation, 191 parts of cyclohexyl methacrylates, styrene 5 parts of 10 parts, 2 parts of acrylic acid and Perbutyl PV, 189.5 parts of toluene, 63 parts of butyl acetate mixed liquor, then it is small with about 1 When instill 5 parts of Perbutyl PV, 70 parts of toluene mixed liquor, continue stir about 1 hour, then cool to room temperature, contained There is the polymer composition (P-2) of modified chlorinated polyolefin.Obtained polymer composition (the P- containing modified chlorinated polyolefin 2) solid component is about 46%, and about 45 parts of 2- allyloxyethanol is contained in composition.The hydroxyl value of resin solid content is About 11mgKOH/g.In addition, chlorinated polyolefin hydrocarbon skeleton in composition with obtained by a part copolymerization of 2- allyloxyethanol The ingredient ratio of acrylic resin skeleton is about 20/80.
Embodiment 3
" ス ー パ ー Network ロ Application 3228S is packed into the four-necked bottle with cooling tube " (trade name, Nippon Paper society system, Maleic anhydride modified chloridized polyolefin, rate containing chlorine 28%) 100 parts, 210 parts of toluene, 11 parts of butyl acetate, di-t-butyl hydroxyl 0.05 part of toluene (referred to as: BHT), stirs while being blown into air into liquid phase, is warming up to about 95 DEG C, solution is made.Xiang Qi 57.5 parts and 0.1 part of tetrabutylammonium bromide of middle addition 2- allyloxyethanol, make 2- allyloxyethanol and anhydride group anti-on one side It should continue to stir on one side.In the infrared absorptiometric analysis of solid component in the solution, in about 1770cm-1Absorbance with about 1460cm-1Absorbance ratio substantially constantization stage, be cooled to about 90 DEG C, obtain containing have allyloxy and hydroxyl About 55 parts of 2- allyloxyethanol of compound (a) i.e. and the concentration of chloridized polyolefin (b) with allyloxy be about 27% Solution.Then, stop being blown into air into liquid phase, exist about 90 DEG C while flowing into nitrogen into gas phase and continue to stir, make For the compound (c) selected from one or more of (methyl) acrylate, (methyl) acrylic acid and styrene, instilled with about 4 hours 205 parts of methyl methacrylate, 183 parts of cyclohexyl methacrylate, 8 parts of methacrylic acid, ethylene glycol dimethacrylate 4 Part and 5 parts of Perbutyl PV, 189.5 parts of toluene, 63 parts of butyl acetate mixed liquor, then with about 1 hour instillation The mixed liquor of 5 parts of Perbutyl PV, 70 parts of toluene continue stir about 1 hour, then cool to room temperature, and obtain containing modification The polymer composition (P-3) of chloridized polyolefin.Obtained polymer composition (P-3's) containing modified chlorinated polyolefin consolidates Body ingredient is about 46%, and about 45 parts of 2- allyloxyethanol is contained in composition.The hydroxyl value of resin solid content is about 11mgKOH/g.In addition, the chlorinated polyolefin hydrocarbon skeleton in composition is copolymerized obtain third with by a part of 2- allyloxyethanol The ingredient ratio of olefin(e) acid resin matrix is about 20/80.
Embodiment 4
" ハ ー De レ Application F-6P is packed into the four-necked bottle with cooling tube " (society's system, maleic anhydride spin in trade name, Japan Modified chloridized polyolefin, rate containing chlorine 20%) 50 parts, 214 parts of toluene, 0.05 part of di-tert-butyl hydroxy toluene (referred to as: BHT), It is stirred while being blown into air into liquid phase, is warming up to about 95 DEG C, solution is made.2- allyloxyethanol 65 is added thereto Part and 0.1 part of tetrabutylammonium bromide, continue to stir while reacting 2- allyloxyethanol with anhydride group.In the solution In the infrared absorptiometric analysis of solid component, in about 1770cm-1Absorbance and about 1460cm-1Absorbance ratio substantially not The stage of variation is cooled to about 90 DEG C, obtains containing compound (a) the i.e. 2- allyloxyethanol with allyloxy and hydroxyl About 64 parts and with allyloxy chloridized polyolefin (b) concentration be about 16% solution.Then, stop blowing into liquid phase Enter air, exists about 90 DEG C while flowing into nitrogen into gas phase and continue to stir, as selected from (methyl) acrylate, (methyl) The compound (c) of one or more of acrylic acid and styrene, with about 4 hours instillations 214 parts of methyl methacrylates, methyl-prop 222 parts of olefin(e) acid cyclohexyl, 10 parts of styrene, 2 parts of acrylic acid, 2 parts of ethylene glycol dimethacrylate and Perbutyl PV 5 parts, 189.5 parts of toluene, 63 parts of butyl acetate mixed liquor, then with about 1 hour 5 parts of Perbutyl PV of instillation, 70 parts of toluene Mixed liquor, continue stir about 1 hour, then cool to room temperature, obtain the polymer composition containing modified chlorinated polyolefin (P-4).The solid component of the obtained polymer composition (P-4) containing modified chlorinated polyolefin is about 46%, in composition Contain about 52 parts of 2- allyloxyethanol.The hydroxyl value of resin solid content is about 12mgKOH/g.In addition, the chlorine in composition The ingredient ratio for changing polyolefin backbone and the acrylic resin skeleton obtained by a part copolymerization of 2- allyloxyethanol is about 10/ 90。
Embodiment 5
100 parts of the loading " ス ー パ ー Network ロ Application 822S into the four-necked bottle with cooling tube ", 221 parts of toluene, two tertiary fourths 0.05 part of base hydroxy-methylbenzene (referred to as: BHT), stirs while being blown into air into liquid phase, is warming up to about 95 DEG C, is made molten Liquid.82.5 parts and 0.1 part of tetrabutylammonium bromide of diglycol monotertiary allyl ether are added thereto, makes diglycol monotertiary allyl ether on one side It is reacted with anhydride group and continues to stir on one side.In the infrared absorptiometric analysis of solid component in the solution, in about 1770cm-1Extinction Degree and about 1460cm-1Absorbance ratio substantially constantization stage, be cooled to about 90 DEG C, obtain containing have allyloxy With about 79 parts of the diglycol monotertiary allyl ether of compound (a) i.e. of hydroxyl and the concentration of the chloridized polyolefin (b) with allyloxy It is about 25% solution.Then, stop being blown into air into liquid phase, exist about 90 DEG C of continuation while flowing into nitrogen into gas phase Stirring, as the compound (c) selected from one or more of (methyl) acrylate, (methyl) acrylic acid and styrene, with about 4 Hour instills 187 parts of methyl methacrylate, 189 parts of cyclohexyl methacrylate, 20 parts of styrene, 2 parts of acrylic acid, ethylene glycol 5 parts of 2 parts of dimethylacrylate and Perbutyl PV, 189.5 parts of toluene, 39 parts of butyl acetate mixed liquor, then with about The mixed liquor of 5 parts of Perbutyl PV, 70 parts of toluene is instilled within 1 hour, is continued stir about 1 hour, is then cooled to room temperature, obtain Polymer composition (P-5) containing modified chlorinated polyolefin.The obtained polymer composition containing modified chlorinated polyolefin (P-5) solid component is about 47%, and about 65 parts of diglycol monotertiary allyl ether is contained in composition.The hydroxyl of resin solid content Value is about 15mgKOH/g.In addition, the chlorinated polyolefin hydrocarbon skeleton in composition is copolymerized with by a part of diglycol monotertiary allyl ether The ingredient ratio of obtained acrylic resin skeleton is about 19/81.
Embodiment 6
100 parts of the loading " ス ー パ ー Network ロ Application 822S into the four-necked bottle with cooling tube ", 228 parts of toluene, two tertiary fourths 0.05 part of base hydroxy-methylbenzene (referred to as: BHT), stirs while being blown into air into liquid phase, is warming up to about 95 DEG C, is made molten Liquid.46 parts of 2- allyloxyethanol of addition, 4 parts of butanol and 0.1 part of tetrabutylammonium bromide thereto, make 2- allyloxy on one side Ethyl alcohol, butanol and anhydride group reaction continue to stir on one side.In the infrared absorptiometric analysis of solid component in the solution, about 1770cm-1Absorbance and about 1460cm-1Absorbance ratio substantially constantization stage, be cooled to about 90 DEG C, contained There is about 44 parts of 2- allyloxyethanol of the compound (a) i.e. with allyloxy and hydroxyl and the chlorination with allyloxy gathers The solution that the concentration of alkene (b) is about 27%.The budgetary estimate molar ratio of the 2- allyloxyethanol and butanol that react with anhydride group is 0.8/0.2.Then, stop being blown into air into liquid phase, exist about 90 DEG C while flowing into nitrogen into gas phase and continue to stir, make For the compound (c) selected from one or more of (methyl) acrylate, (methyl) acrylic acid and styrene, instilled with about 4 hours 197 parts of methyl methacrylate, 189 parts of cyclohexyl methacrylate, 10 parts of styrene, 2 parts of acrylic acid, ethylene glycol dimethyl third 5 parts of 2 parts of olefin(e) acid ester and Perbutyl PV, 189.5 parts of toluene, 63 parts of butyl acetate mixed liquor, then dripped with about 1 hour Enter the mixed liquor of 5 parts of Perbutyl PV, 70 parts of toluene, continue stir about 1 hour, then cool to room temperature, obtains containing changing The polymer composition (P-6) of property chloridized polyolefin.The obtained polymer composition (P-6) containing modified chlorinated polyolefin Solid component is about 46%, and about 36 parts of 2- allyloxyethanol is contained in composition.The hydroxyl value of resin solid content is about 9mgKOH/g.In addition, the chlorinated polyolefin hydrocarbon skeleton in composition is copolymerized obtain third with by a part of 2- allyloxyethanol The ingredient ratio of olefin(e) acid resin matrix is about 20/80.
Embodiment 7
100 parts of the loading " ス ー パ ー Network ロ Application 822S into the four-necked bottle with cooling tube ", 70 parts of toluene, di-t-butyl 0.05 part of hydroxy-methylbenzene (referred to as: BHT), stirs while being blown into air into liquid phase, is warming up to about 95 DEG C, solution is made. 11.5 parts of 2- allyloxyethanol of addition, 17 parts of butanol and 0.1 part of tetrabutylammonium bromide thereto, make 2- allyloxy on one side Ethyl alcohol, butanol and anhydride group reaction continue to stir on one side.In the infrared absorptiometric analysis of solid component in the solution, about 1770cm-1Absorbance and about 1460cm-1Absorbance ratio substantially constantization stage, be cooled to about 90 DEG C, further 140 parts and 39 parts of 2- allyloxyethanol of toluene are added, is obtained containing compound (a) the i.e. 2- alkene with allyloxy and hydroxyl The solution that the concentration of about 50 parts of allyloxyethanol and the chloridized polyolefin (b) with allyloxy is about 27%.It is anti-with anhydride group The budgetary estimate molar ratio of the 2- allyloxyethanol and butanol answered is 0.2/0.8.Then, stop being blown into air into liquid phase, on one side It flows into nitrogen into gas phase to continue to stir at about 90 DEG C on one side, as selected from (methyl) acrylate, (methyl) acrylic acid and benzene The compound (c) of one or more of ethylene, with about 4 hours instillations 206 parts of methyl methacrylates, cyclohexyl methacrylate 5 parts of 189 parts, 3 parts of methacrylic acid, 2 parts of ethylene glycol dimethacrylate and Perbutyl PV, 189.5 parts of toluene, The mixed liquor that 63 parts of butyl acetate, then with about 1 hour instill 5 parts of Perbutyl PV, 70 parts of toluene mixed liquor, continue to stir It about 1 hour, then cools to room temperature, obtains the polymer composition (P-7) containing modified chlorinated polyolefin.Containing for obtaining changes Property chloridized polyolefin the solid component of polymer composition (P-7) be about 46%, about 42 parts of 2- allyl is contained in composition Ethoxy-ethanol.The hydroxyl value of resin solid content is about 10mgKOH/g.In addition, chlorinated polyolefin hydrocarbon skeleton in composition with by 2- The ingredient ratio for the acrylic resin skeleton that a part copolymerization of allyloxyethanol obtains is about 20/80.
Embodiment 8
100 parts of the loading " ス ー パ ー Network ロ Application 3228S into the four-necked bottle with cooling tube ", 70 parts of toluene, two tertiary fourths 0.05 part of base hydroxy-methylbenzene (referred to as: BHT), stirs while being blown into air into liquid phase, is warming up to about 95 DEG C, is made molten Liquid.11.5 parts of 2- allyloxyethanol of addition, 16 parts of butanol, 1 part of 2-Ethylhexyl Alcohol and 0.1 part of tetrabutylammonium bromide thereto, Continue to stir while reacting 2- allyloxyethanol, butanol, 2-Ethylhexyl Alcohol and anhydride group.Solid in the solution at In the infrared absorptiometric analysis divided, in about 1770cm-1Absorbance and about 1460cm-1Absorbance ratio substantially constantization Stage is cooled to about 90 DEG C, further adds 140 parts and 39 parts of 2- allyloxyethanol of toluene, obtains containing with allyl oxygen The concentration of about 50 parts of 2- allyloxyethanol of the compound (a) i.e. of base and hydroxyl and the chloridized polyolefin (b) with allyloxy It is about 27% solution.The budgetary estimate molar ratio of the 2- allyloxyethanol reacted with anhydride group and alcohol in addition to this is 0.2/ 0.8.Then, stop being blown into air into liquid phase, exist about 90 DEG C while flowing into nitrogen into gas phase and continue to stir, as choosing From the compound (c) of one or more of (methyl) acrylate, (methyl) acrylic acid and styrene, with about 4 hours instillation methyl 206 parts of methyl acrylate, 180 parts of cyclohexyl methacrylate, 10 parts of styrene, 2 parts of acrylic acid, ethyleneglycol dimethacrylate 5 parts of 2 parts of ester and Perbutyl PV, 189.5 parts of toluene, 63 parts of butyl acetate mixed liquor, then instilled with about 1 hour The mixed liquor of 5 parts of Perbutyl PV, 70 parts of toluene continue stir about 1 hour, then cool to room temperature, and obtain containing modification The polymer composition (P-8) of chloridized polyolefin.Obtained polymer composition (P-8's) containing modified chlorinated polyolefin consolidates Body ingredient is about 46%, and about 41 parts of 2- allyloxyethanol is contained in composition.The hydroxyl value of resin solid content is about 10mgKOH/g.In addition, the chlorinated polyolefin hydrocarbon skeleton in composition is copolymerized obtain third with by a part of 2- allyloxyethanol The ingredient ratio of olefin(e) acid resin matrix is about 20/80.
Embodiment 9
100 parts of the loading " ス ー パ ー Network ロ Application 822S into the four-necked bottle with cooling tube ", 70 parts of toluene, di-t-butyl 0.05 part of hydroxy-methylbenzene (referred to as: BHT), stirs while being blown into air into liquid phase, is warming up to about 95 DEG C, solution is made. 11.5 parts of 2- allyloxyethanol of addition, 1 part of acrylic acid 4- hydroxybutyl and 0.1 part of tetrabutylammonium bromide thereto, make on one side 2- allyloxyethanol, acrylic acid 4- hydroxybutyl and anhydride group reaction continue to stir on one side.Solid component in the solution In infrared absorptiometric analysis, in about 1770cm-1Absorbance and about 1460cm-1Absorbance ratio substantially constantization stage, About 90 DEG C are cooled to, 156 parts and 39 parts of 2- allyloxyethanol of toluene is further added, obtains containing with allyloxy and hydroxyl The concentration of about 48 parts of 2- allyloxyethanol of the compound (a) i.e. of base and the chloridized polyolefin (b) with allyloxy is about 27% solution.The budgetary estimate molar ratio of the 2- allyloxyethanol and acrylic acid 4- hydroxybutyl that react with anhydride group is 0.9/ 0.1.Then, stop being blown into air into liquid phase, exist about 90 DEG C while flowing into nitrogen into gas phase and continue to stir, as choosing From the compound (c) of one or more of (methyl) acrylate, (methyl) acrylic acid and styrene, with about 4 hours instillation methyl 303 parts of methyl acrylate, 96 parts of cyclohexyl methacrylate, 1 part of acrylic acid and 5 parts of Perbutyl PV, toluene 189.5 Part, 63 parts of butyl acetate of mixed liquor, then instilled with about 1 hour the mixed liquor of 5 parts of Perbutyl PV, 70 parts of toluene, continuation It stir about 1 hour, then cools to room temperature, obtains the polymer composition (P-9) containing modified chlorinated polyolefin.What is obtained contains The solid component for having the polymer composition (P-9) of modified chlorinated polyolefin is about 46%, and about 39 parts of 2- is contained in composition Allyloxyethanol.The hydroxyl value of resin solid content is about 10mgKOH/g.In addition, chlorinated polyolefin hydrocarbon skeleton in composition with The ingredient ratio of the acrylic resin skeleton obtained by a part copolymerization of 2- allyloxyethanol is about 20/80.
Embodiment 10
50 parts of the loading " ハ ー De レ Application F-6P into the four-necked bottle with cooling tube ", 70 parts of toluene, di-t-butyl hydroxyl 0.05 part of toluene (referred to as: BHT), stirs while being blown into air into liquid phase, is warming up to about 95 DEG C, solution is made.Xiang Qi Middle 1.3 parts of addition 2- allyloxyethanol, 3 parts of 2-hydroxyethyl methacrylate, 4 parts of butanol and tetrabutylammonium bromide 0.1 Part, continue to stir while reacting 2- allyloxyethanol, 2-hydroxyethyl methacrylate, butanol and anhydride group.? In the infrared absorptiometric analysis of solid component in solution, in about 1770cm-1Absorbance and about 1460cm-1Absorbance ratio The stage of substantially constantization is cooled to about 90 DEG C, further adds 140 parts and 60 parts of 2- allyloxyethanol of toluene, obtains Containing about 61 parts of 2- allyloxyethanol of the compound (a) i.e. with allyloxy and hydroxyl and with the chlorination of allyloxy The solution that the concentration of polyolefin (b) is about 16%.The 2- allyloxyethanol that is reacted with anhydride group, methacrylic acid 2- hydroxyl second The budgetary estimate molar ratio of ester and butanol is 0.1/0.1/0.8.Then, stop being blown into air into liquid phase, be flowed on one side into gas phase Nitrogen continues to stir at about 90 DEG C on one side, as a kind selected from (methyl) acrylate, in (methyl) acrylic acid and styrene with On compound (c), with about 4 hours 90 parts of methyl methacrylates of instillation, 352 parts of cyclohexyl methacrylates, styrene 5 Part, 5 parts of 3 parts of acrylic acid and Perbutyl PV, 189.5 parts of toluene, 63 parts of butyl acetate mixed liquor, then with about 1 hour The mixed liquor of 5 parts of Perbutyl PV, 70 parts of toluene is instilled, is continued stir about 1 hour, is then cooled to room temperature, contained The polymer composition (P-10) of modified chlorinated polyolefin.Obtained polymer composition (the P- containing modified chlorinated polyolefin 10) solid component is about 46%, and about 49 parts of 2- allyloxyethanol is contained in composition.The hydroxyl value of resin solid content is About 14mgKOH/g.In addition, chlorinated polyolefin hydrocarbon skeleton in composition with obtained by a part copolymerization of 2- allyloxyethanol The ingredient ratio of acrylic resin skeleton is about 10/90.
Embodiment 11
100 parts of the loading " ス ー パ ー Network ロ Application 3228S into the four-necked bottle with cooling tube ", 221 parts of toluene, two tertiary fourths 0.05 part of base hydroxy-methylbenzene (referred to as: BHT), stirs while being blown into air into liquid phase, is warming up to about 95 DEG C, is made molten Liquid.40 parts of 2- allyloxyethanol of addition, 15 parts of butanol and 0.1 part of tetrabutylammonium bromide thereto, make 2- allyloxy on one side Ethyl alcohol, butanol and anhydride group reaction continue to stir on one side.In the infrared absorptiometric analysis of solid component in the solution, about 1770cm-1Absorbance and about 1460cm-1Absorbance ratio substantially constantization stage, be cooled to about 90 DEG C, contained There is about 39 parts of 2- allyloxyethanol of the compound (a) i.e. with allyloxy and hydroxyl and the chlorination with allyloxy gathers The solution that the concentration of alkene (b) is about 27%.The budgetary estimate molar ratio of the 2- allyloxyethanol and butanol that react with anhydride group is 0.5/0.5.Then, stop being blown into air into liquid phase, exist about 90 DEG C while flowing into nitrogen into gas phase and continue to stir, make For the compound (c) selected from one or more of (methyl) acrylate, (methyl) acrylic acid and styrene, instilled with about 4 hours 162 parts of methyl methacrylate, 56 parts of n-butyl acrylate, 144 parts of isophorone acrylate, acrylic acid 2- hydroxy methacrylate 36 Part, 2 parts of ethylene glycol dimethacrylate and 5 parts of Perbutyl PV, 189.5 parts of toluene, 30 parts of butyl acetate, butanol 33 parts of mixed liquor, then with about 1 hour instill 5 parts of Perbutyl PV, 70 parts of toluene mixed liquor, continue stir about 1 hour, It then cools to room temperature, obtains the polymer composition (P-11) containing modified chlorinated polyolefin.Containing for obtaining is modified chlorinated The solid component of the polymer composition (P-11) of polyolefin is about 46%, and about 32 parts of 2- allyloxy second is contained in composition Alcohol.The hydroxyl value of resin solid content is about 42mgKOH/g.In addition, chlorinated polyolefin hydrocarbon skeleton in composition with by 2- allyl oxygen The ingredient ratio for the acrylic resin skeleton that a part copolymerization of base ethyl alcohol obtains is about 20/80.
Embodiment 12
100 parts of the loading " ス ー パ ー Network ロ Application 822S into the four-necked bottle with cooling tube ", 70 parts of toluene, di-t-butyl 0.05 part of hydroxy-methylbenzene (referred to as: BHT), stirs while being blown into air into liquid phase, is warming up to about 95 DEG C, solution is made. 30 parts of 2- allyloxyethanol and 0.1 part of tetrabutylammonium bromide are added thereto, makes 2- allyloxyethanol and anhydride group on one side Reaction continues to stir on one side.In the infrared absorptiometric analysis of solid component in the solution, in about 1770cm-1Absorbance with about 1460cm-1Absorbance ratio substantially constantization stage, be cooled to about 90 DEG C, further addition 178 parts of toluene, contained There is about 28 parts of 2- allyloxyethanol of the compound (a) i.e. with allyloxy and hydroxyl and the chlorination with allyloxy gathers The solution that the concentration of alkene (b) is about 27%.Then, stop being blown into air into liquid phase, flow into nitrogen one into gas phase on one side 90 DEG C of Bian Yue are continued to stir, as the change selected from one or more of (methyl) acrylate, (methyl) acrylic acid and styrene It closes object (c), with about 4 hours 303 parts of cyclohexyl methacrylates of instillation, 84 parts of n-butyl acrylates, acrylic acid 2- hydroxy methacrylate 5 parts of 10 parts, 3 parts of methacrylic acid and Perbutyl PV, 189.5 parts of toluene, 45 parts of butyl acetate, 18 parts of butanol it is mixed Liquid is closed, then instilled the mixed liquor of 5 parts of Perbutyl PV, 70 parts of toluene with about 1 hour, continues stir about 1 hour, then cools down To room temperature, the polymer composition (P-12) containing modified chlorinated polyolefin is obtained.Obtain containing modified chlorinated polyolefin The solid component of polymer composition (P-12) is about 46%, and about 23 parts of 2- allyloxyethanol is contained in composition.Resin The hydroxyl value of solid component is about 15mgKOH/g.In addition, chlorinated polyolefin hydrocarbon skeleton in composition with by 2- allyloxyethanol The ingredient ratio for the acrylic resin skeleton that a part copolymerization obtains is about 20/80.
Embodiment 13
100 parts of the loading " ハ ー De レ Application F-6P into the four-necked bottle with cooling tube ", 70 parts of toluene, di-t-butyl hydroxyl 0.05 part of toluene (referred to as: BHT), stirs while being blown into air into liquid phase, is warming up to about 95 DEG C, solution is made.Xiang Qi Middle 11.5 parts of addition 2- allyloxyethanol, 3 parts of 2-hydroxyethyl methacrylate and 0.1 part of tetrabutylammonium bromide, make on one side 2- allyloxyethanol, 2-hydroxyethyl methacrylate and anhydride group reaction continue to stir on one side.Solid in the solution at In the infrared absorptiometric analysis divided, in about 1770cm-1Absorbance and about 1460cm-1Absorbance ratio substantially constantization Stage is cooled to about 90 DEG C, further 193 parts of toluene of addition, obtains containing the compound (a) with allyloxy and hydroxyl i.e. The solution that the concentration of about 9 parts of 2- allyloxyethanol and the chloridized polyolefin (b) with allyloxy is about 27%.With acid anhydrides The 2- allyloxyethanol of base reaction and the budgetary estimate molar ratio of 2-hydroxyethyl methacrylate are 0.9/0.1.Then, stop to It is blown into air in liquid phase, exists about 90 DEG C while flowing into nitrogen into gas phase and continues to stir, as selected from (methyl) acrylic acid The compound (c) of one or more of ester, (methyl) acrylic acid and styrene, with about 4 hours instillation methyl methacrylates 175 Part, 195 parts of cyclohexyl methacrylate, 26 parts of 2-hydroxyethyl methacrylate, 4 parts of acrylic acid and Perbutyl PV 5 Part, 189.5 parts of toluene, 33 parts of butyl acetate, 30 parts of butanol mixed liquor, then with about 1 hour 5 parts of Perbutyl PV of instillation, The mixed liquor that 70 parts of toluene continues stir about 1 hour, then cools to room temperature, obtain the polymerization containing modified chlorinated polyolefin Compositions (P-13).The solid component of the obtained polymer composition (P-13) containing modified chlorinated polyolefin is about 45%, about 8 parts of 2- allyloxyethanol is contained in composition.The hydroxyl value of resin solid content is about 26mgKOH/g.In addition, Chlorinated polyolefin hydrocarbon skeleton in composition is copolymerized obtained acrylic resin skeleton with by a part of 2- allyloxyethanol Ingredient ratio is about 20/80.
Embodiment 14
150 parts of the loading " ス ー パ ー Network ロ Application 822S into the four-necked bottle with cooling tube ", 105 parts of toluene, two tertiary fourths 0.05 part of base hydroxy-methylbenzene (referred to as: BHT), stirs while being blown into air into liquid phase, is warming up to about 95 DEG C, is made molten Liquid.18 parts of 2- allyloxyethanol of addition, 3 parts of butanol and 0.1 part of tetrabutylammonium bromide thereto, make 2- allyloxy on one side Ethyl alcohol, butanol and anhydride group reaction continue to stir on one side.In the infrared absorptiometric analysis of solid component in the solution, about 1770cm-1Absorbance and about 1460cm-1Absorbance ratio substantially constantization stage, be cooled to about 90 DEG C, further 255 parts of toluene of addition, obtain containing about 14 parts of the 2- allyloxyethanol of compound (a) i.e. with allyloxy and hydroxyl and The solution that the concentration of chloridized polyolefin (b) with allyloxy is about 29%.The 2- allyloxyethanol reacted with anhydride group Budgetary estimate molar ratio with butanol is 0.7/0.3.Then, stop being blown into air into liquid phase, flow into nitrogen one into gas phase on one side 90 DEG C of Bian Yue are continued to stir, as the change selected from one or more of (methyl) acrylate, (methyl) acrylic acid and styrene It closes object (c), with about 4 hours 250 parts of cyclohexyl methacrylates of instillation, 48 parts of isophorone acrylate, methacrylic acid 2- 5 parts of 22 parts of hydroxy methacrylate, 30 parts of styrene and Perbutyl PV, 82.5 parts of toluene, 38 parts of butyl acetate, 27 parts of butanol Mixed liquor, then with about 1 hour instill 5 parts of Perbutyl PV, 70 parts of toluene mixed liquor, continue stir about 1 hour, then It is cooled to room temperature, obtains the polymer composition (P-14) containing modified chlorinated polyolefin.What is obtained contains modified chlorinated polyene The solid component of the polymer composition (P-14) of hydrocarbon is about 45%, and about 12 parts of 2- allyloxyethanol is contained in composition. The hydroxyl value of resin solid content is about 22mgKOH/g.In addition, chlorinated polyolefin hydrocarbon skeleton in composition with by 2- allyloxy second The ingredient ratio for the acrylic resin skeleton that a part copolymerization of alcohol obtains is about 30/70.
Embodiment 15
100 parts of the loading " ス ー パ ー Network ロ Application 822S into the four-necked bottle with cooling tube ", 70 parts of toluene, di-t-butyl 0.05 part of hydroxy-methylbenzene (referred to as: BHT), stirs while being blown into air into liquid phase, is warming up to about 95 DEG C, solution is made. 23 parts and 0.1 part of tetrabutylammonium bromide of 2- allyloxyethanol are added thereto, makes 2- allyloxyethanol and anhydride group on one side Reaction continues to stir on one side.In the infrared absorptiometric analysis of solid component in the solution, in about 1770cm-1Absorbance with about 1460cm-1Absorbance ratio substantially constantization stage, be cooled to about 90 DEG C, 150 parts of toluene and 2- alkene be further added It 34.5 parts of allyloxyethanol, thus obtains containing compound (a) the i.e. 2- allyloxyethanol with allyloxy and hydroxyl about 55 parts and with allyloxy chloridized polyolefin (b) concentration be about 27% solution.Then, stop being blown into liquid phase Air exists about 90 DEG C while flowing into nitrogen into gas phase and continues to stir, as selected from (methyl) acrylate, (methyl) third The compound (c) of one or more of olefin(e) acid and styrene, with about 4 hours instillations 197 parts of methyl methacrylates, metering system 191 parts of sour cyclohexyl, 10 parts of styrene, 2 parts of acrylic acid and Perhexa25O (trade name, You society system, 2,5- dimethyl- The 50% hydrocarbon solution of 2,5- bis- (2- ethyihexanoylperoxy) hexane) 12 parts of (6 parts of effective components), 189.5 parts of toluene, butyl acetate 63 parts of mixed liquor, then with about 1 hour instill 6 parts of Perhexa25O, 70 parts of toluene mixed liquor, continue stir about 1 hour, It then cools to room temperature, obtains the polymer composition (P-15) containing modified chlorinated polyolefin.Containing for obtaining is modified chlorinated The solid component of the polymer composition (P-15) of polyolefin is about 46%, and about 45 parts of 2- allyloxy second is contained in composition Alcohol.The hydroxyl value of resin solid content is about 11mgKOH/g.In addition, chlorinated polyolefin hydrocarbon skeleton in composition with by 2- allyl oxygen The ingredient ratio for the acrylic resin skeleton that a part copolymerization of base ethyl alcohol obtains is about 20/80.
Embodiment 16
100 parts of the loading " ス ー パ ー Network ロ Application 822S into the four-necked bottle with cooling tube ", 70 parts of toluene, di-t-butyl 0.05 part of hydroxy-methylbenzene (referred to as: BHT), stirs while being blown into air into liquid phase, is warming up to about 95 DEG C, solution is made. 23 parts and 0.1 part of tetrabutylammonium bromide of 2- allyloxyethanol are added thereto, makes 2- allyloxyethanol and anhydride group on one side Reaction continues to stir on one side.In the infrared absorptiometric analysis of solid component in the solution, in about 1770cm-1Absorbance with about 1460cm-1Absorbance ratio substantially constantization stage, be cooled to about 90 DEG C, 150 parts of toluene and 2- alkene be further added It 34.5 parts of allyloxyethanol, thus obtains containing compound (a) the i.e. 2- allyloxyethanol with allyloxy and hydroxyl about 55 parts and with allyloxy chloridized polyolefin (b) concentration be about 27% solution.Then, stop being blown into liquid phase Air exists about 90 DEG C while flowing into nitrogen into gas phase and continues to stir, as selected from (methyl) acrylate, (methyl) third The compound (c) of one or more of olefin(e) acid and styrene, with about 4 hours instillations 197 parts of methyl methacrylates, metering system 191 parts of sour cyclohexyl, 10 parts of styrene, 2 parts of acrylic acid and V-65 (trade name, He Guangchun medicine society system, azo bis- (2,4- bis- Methyl valeronitrile)) 5 parts, the mixed liquor of 189.5 parts of toluene, 63 parts of butyl acetate, then with about 1 hour instillation Perbutyl PV 5 Part, 70 parts of toluene of mixed liquor, continue stir about 1 hour, then cool to room temperature, and obtain poly- containing modified chlorinated polyolefin Polymer composition (P-16).The solid component of the obtained polymer composition (P-16) containing modified chlorinated polyolefin is about 46%, about 45 parts of 2- allyloxyethanol is contained in composition.The hydroxyl value of resin solid content is about 11mgKOH/g.In addition, Chlorinated polyolefin hydrocarbon skeleton in composition is copolymerized obtained acrylic resin skeleton with by a part of 2- allyloxyethanol Ingredient ratio is about 20/80.
Embodiment 17
100 parts of the loading " ス ー パ ー Network ロ Application 822S into the four-necked bottle with cooling tube ", 67 parts of toluene, methyl cyclohexane 3 parts of alkane, 0.05 part of di-tert-butyl hydroxy toluene (referred to as: BHT), stir while being blown into air into liquid phase, are warming up to about 95 DEG C, solution is made.23 parts and 0.1 part of tetrabutylammonium bromide of 2- allyloxyethanol are added thereto, makes 2- allyl oxygen on one side Base ethyl alcohol is reacted with anhydride group to be continued to stir on one side.In the infrared absorptiometric analysis of solid component in the solution, in about 1770cm-1 Absorbance and about 1460cm-1Absorbance ratio substantially constantization stage, be cooled to about 90 DEG C, toluene be further added Thus 145 parts, 5 parts of hexahydrotoluene and 34.5 parts of 2- allyloxyethanol are obtained containing the change with allyloxy and hydroxyl Close object (a) i.e. about 55 parts of 2- allyloxyethanol and with allyloxy chloridized polyolefin (b) concentration be about 27% it is molten Liquid.Then, stop being blown into air into liquid phase, exist about 90 DEG C while flowing into nitrogen into gas phase and continue to stir, as choosing From the compound (c) of one or more of (methyl) acrylate, (methyl) acrylic acid and styrene, with about 4 hours instillation methyl 197 parts of methyl acrylate, 191 parts of cyclohexyl methacrylate, 10 parts of styrene, 2 parts of acrylic acid and Perbutyl PV 5 Part, 171.5 parts of toluene, 18 parts of hexahydrotoluene, 63 parts of butyl acetate mixed liquor, then with about 1 hour instillation Perbutyl PV 5 parts, 63 parts of toluene, 7 parts of hexahydrotoluene mixed liquor, continue stir about 1 hour, then cool to room temperature, obtain containing changing The polymer composition (P-17) of property chloridized polyolefin.The obtained polymer composition (P-17) containing modified chlorinated polyolefin Solid component be about 46%, about 45 parts of 2- allyloxyethanol is contained in composition.The hydroxyl value of resin solid content is about 11mgKOH/g.In addition, the chlorinated polyolefin hydrocarbon skeleton in composition is copolymerized obtain third with by a part of 2- allyloxyethanol The ingredient ratio of olefin(e) acid resin matrix is about 20/80.
Embodiment 18
100 parts of the loading " ス ー パ ー Network ロ Application 822S into the four-necked bottle with cooling tube ", 70 parts of toluene, di-t-butyl 0.05 part of hydroxy-methylbenzene (referred to as: BHT), stirs while being blown into air into liquid phase, is warming up to about 95 DEG C, solution is made. 23 parts and 0.1 part of tetrabutylammonium bromide of 2- allyloxyethanol are added thereto, makes 2- allyloxyethanol and anhydride group on one side Reaction continues to stir on one side.In the infrared absorptiometric analysis of solid component in the solution, in about 1770cm-1Absorbance with about 1460cm-1Absorbance ratio substantially constantization stage, be cooled to about 90 DEG C, 150 parts of toluene and 2- alkene be further added It 34.5 parts of allyloxyethanol, thus obtains containing compound (a) the i.e. 2- allyloxyethanol with allyloxy and hydroxyl about 55 parts and with allyloxy chloridized polyolefin (b) concentration be about 27% solution.Then, stop being blown into liquid phase Air exists about 90 DEG C while flowing into nitrogen into gas phase and continues to stir, as selected from (methyl) acrylate, (methyl) third The compound (c) of one or more of olefin(e) acid and styrene, with about 4 hours instillations 197 parts of methyl methacrylates, metering system 5 parts of 191 parts of sour cyclohexyl, 10 parts of styrene, 2 parts of acrylic acid and Perbutyl PV, 171.5 parts of toluene, 9 parts of hexamethylene, The mixed liquor of 9 parts of hexahydrotoluene, 63 parts of butyl acetate, then with about 1 hour 5 parts of Perbutyl PV of instillation, 63 parts of toluene, ring The mixed liquor of 3 parts of hexane, 4 parts of hexahydrotoluene continues stir about 1 hour, then cools to room temperature, obtain containing modified chlorinated The polymer composition (P-18) of polyolefin.The solid of the obtained polymer composition (P-18) containing modified chlorinated polyolefin Ingredient is about 46%, and about 45 parts of 2- allyloxyethanol is contained in composition.The hydroxyl value of resin solid content is about 11mgKOH/g.In addition, the chlorinated polyolefin hydrocarbon skeleton in composition is copolymerized obtain third with by a part of 2- allyloxyethanol The ingredient ratio of olefin(e) acid resin matrix is about 20/80.
Comparative example 1
100 parts of the loading " ス ー パ ー Network ロ Application 822S into the four-necked bottle with cooling tube ", 221 parts of toluene, two tertiary fourths 0.05 part of base hydroxy-methylbenzene (referred to as: BHT), stirs while being blown into air into liquid phase, is warming up to about 95 DEG C, is made molten Liquid.57.5 parts of 2-hydroxyethyl methacrylate and 0.1 part of tetrabutylammonium bromide are added thereto, makes methacrylic acid on one side 2- hydroxy methacrylate and anhydride group reaction continue to stir on one side.In the infrared absorptiometric analysis of solid component in the solution, about 1770cm-1Absorbance and about 1460cm-1Absorbance ratio substantially constantization stage, be cooled to about 90 DEG C, obtain not The solution that the concentration of chloridized polyolefin (b) with allyloxy is about 27%.Then, stop being blown into air into liquid phase, one While into gas phase flow into nitrogen on one side continue to stir at about 90 DEG C, as selected from (methyl) acrylate, (methyl) acrylic acid and The compound (c) of one or more of styrene instills 197 parts of methyl methacrylate, 189 parts of cyclohexyl methacrylate, benzene 5 parts of 10 parts of ethylene, 2 parts of ethylene glycol dimethacrylate, 2 parts of acrylic acid and Perbutyl PV, 189.5 parts of toluene, second The mixed liquor that 63 parts of acid butyl ester, as a result, about 1 hour after instillation starts, gelatine occurs for reaction system, therefore stops to contain and change The manufacture of the polymer composition of property chloridized polyolefin.
Comparative example 2
100 parts of the loading " ス ー パ ー Network ロ Application 3228S into the four-necked bottle with cooling tube ", 70 parts of toluene, two tertiary fourths 0.05 part of base hydroxy-methylbenzene (referred to as: BHT), stirs while being blown into air into liquid phase, is warming up to about 95 DEG C, is made molten Liquid.23 parts of 2-hydroxyethyl methacrylate and 0.1 part of tetrabutylammonium bromide are added thereto, makes methacrylic acid 2- on one side 23 parts of hydroxy methacrylate and anhydride group reaction continue to stir on one side.About after forty minutes, system is generated heat suddenly, start to polymerize, therefore Stop the manufacture of the polymer composition containing modified chlorinated polyolefin.
Comparative example 3
100 parts of the loading " ス ー パ ー Network ロ Application 822S into the four-necked bottle with cooling tube ", 218 parts of toluene, two tertiary fourths 0.05 part of base hydroxy-methylbenzene (referred to as: BHT), stirs while being blown into air into liquid phase, is warming up to about 95 DEG C, is made molten Liquid.57.5 parts of 2-hydroxyethyl methacrylate of addition, 2 parts of butanol and 0.1 part of tetrabutylammonium bromide thereto, make first on one side Base acrylic acid 2- hydroxy methacrylate, butanol and anhydride group reaction continue to stir on one side.The infrared extinction of solid component in the solution In analysis, in about 1770cm-1Absorbance and about 1460cm-1Absorbance ratio substantially constantization stage, be cooled to about 90 DEG C, obtain the solution that the concentration of the chloridized polyolefin (b) without allyloxy is about 27%.The methyl reacted with anhydride group The budgetary estimate molar ratio of acrylic acid 2- hydroxy methacrylate and butanol is 0.8/0.2.Then, stop being blown into air into liquid phase, on one side to It flows into nitrogen in gas phase to continue to stir at about 90 DEG C on one side, as selected from (methyl) acrylate, (methyl) acrylic acid and benzene second The compound (c) of one or more of alkene instills 197 parts of methyl methacrylate, 186 parts of cyclohexyl methacrylate, acrylic acid 5 parts of 6 parts of 2- hydroxy methacrylate, 10 parts of styrene, 1 part of acrylic acid and Perbutyl PV, 189.5 parts of toluene, butyl acetate 63 The mixed liquor of part, as a result, about 1 hour after instillation starts, gelatine occurs for reaction system, therefore stops containing modified chlorinated poly- The manufacture of the polymer composition of alkene.
Comparative example 4
100 parts of the loading " ス ー パ ー Network ロ Application 822S into the four-necked bottle with cooling tube ", 70 parts of toluene, di-t-butyl 0.05 part of hydroxy-methylbenzene (referred to as: BHT), stirs while being blown into air into liquid phase, is warming up to about 95 DEG C, solution is made. 11.5 parts of 2-hydroxyethyl methacrylate of addition, 17 parts of butanol and 0.1 part of tetrabutylammonium bromide thereto, make methyl on one side Acrylic acid 2- hydroxy methacrylate, butanol and anhydride group reaction continue to stir on one side.The infrared extinction of solid component in the solution point In analysis, in about 1770cm-1Absorbance and about 1460cm-1Absorbance ratio substantially constantization stage, be cooled to about 90 DEG C, further 180 parts of toluene of addition, obtains the solution that the concentration of the chloridized polyolefin (b) without allyloxy is about 27%. The budgetary estimate molar ratio of the 2-hydroxyethyl methacrylate and butanol that react with anhydride group is 0.1/0.9.Then, stop to liquid phase In be blown into air, exist about 90 DEG C on one side on one side flowing into nitrogen into gas phase and continue to stir, as be selected from (methyl) acrylate, The compound (c) of one or more of (methyl) acrylic acid and styrene, with about 4 hours 197 parts of methyl methacrylates of instillation, 189 parts of cyclohexyl methacrylate, 2 parts of ethylene glycol dimethacrylate, 10 parts of styrene, 2 parts of acrylic acid, and 5 parts of Perbutyl PV, 189.5 parts of toluene, 63 parts of butyl acetate mixed liquor, then with about 1 hour instillation Perbutyl PV 5 Part, 70 parts of toluene of mixed liquor, continue stir about 1 hour, then cool to room temperature, and obtain poly- containing modified chlorinated polyolefin Polymer composition (P-22).The solid component of the obtained polymer composition (P-22) containing modified chlorinated polyolefin is about 46%, the hydroxyl value of resin solid content is about 9mgKOH/g.In addition, chlorinated polyolefin hydrocarbon skeleton and acrylic resin in composition The ingredient ratio of skeleton is about 20/80.
Comparative example 5
100 parts of the loading " ス ー パ ー Network ロ Application 822S into the four-necked bottle with cooling tube ", 70 parts of toluene, di-t-butyl 0.05 part of hydroxy-methylbenzene (referred to as: BHT), stirs while being blown into air into liquid phase, is warming up to about 95 DEG C, solution is made. 11.5 parts of 2-hydroxyethyl methacrylate of addition, 17 parts of butanol and 0.1 part of tetrabutylammonium bromide thereto, make methyl on one side Acrylic acid 2- hydroxy methacrylate, butanol and anhydride group reaction continue to stir on one side.The infrared extinction of solid component in the solution point In analysis, in about 1770cm-1Absorbance and about 1460cm-1Absorbance ratio substantially constantization stage, be cooled to about 90 DEG C, 172 parts and 6.8 parts of 2-hydroxyethyl methacrylate of toluene are further added, it is poly- to obtain the chlorination without allyloxy The solution that the concentration of alkene (b) is about 27%.The budgetary estimate of the 2-hydroxyethyl methacrylate and butanol that react with anhydride group rubs You are than being 0.1/0.9.Then, stop being blown into air into liquid phase, exist about 90 DEG C of continuation while flowing into nitrogen into gas phase Stirring, as the compound (c) selected from one or more of (methyl) acrylate, (methyl) acrylic acid and styrene, with about 4 Hour instills 206 parts of methyl methacrylate, 189 parts of cyclohexyl methacrylate, 2 parts of ethylene glycol dimethacrylate, first 5 parts of 3 parts of base acrylic acid and Perbutyl PV, 189.5 parts of toluene, 63 parts of butyl acetate mixed liquor, then with about 1 hour The mixed liquor of 5 parts of Perbutyl PV, 70 parts of toluene is instilled, is continued stir about 1 hour, is then cooled to room temperature, contained The polymer composition (P-23) of modified chlorinated polyolefin.Obtained polymer composition (the P- containing modified chlorinated polyolefin 23) solid component is about 46%, and the hydroxyl value of resin solid content is about 15mgKOH/g.In addition, the chlorinated polyolefin in composition The ingredient ratio of hydrocarbon skeleton and acrylic resin skeleton is about 20/80.
Comparative example 6
50 parts of the loading " ハ ー De レ Application F-6P into the four-necked bottle with cooling tube ", 70 parts of toluene, di-t-butyl hydroxyl 0.05 part of toluene (referred to as: BHT), stirs while being blown into air into liquid phase, is warming up to about 95 DEG C, solution is made.Xiang Qi Middle 11.5 parts of addition 2-hydroxyethyl methacrylate, 16 parts of butanol, 1 part of 2-Ethylhexyl Alcohol and 0.1 part of tetrabutylammonium bromide, one While 2-hydroxyethyl methacrylate, butanol, 2-Ethylhexyl Alcohol and anhydride group reaction is made to continue to stir on one side.Consolidating in the solution In the infrared absorptiometric analysis of body ingredient, in about 1770cm-1Absorbance and about 1460cm-1Absorbance ratio it is substantially constant The stage of change is cooled to about 90 DEG C, and further 180 parts of toluene of addition, obtains the chloridized polyolefin (b) without allyloxy The solution that concentration is about 16%.The budgetary estimate mole of the 2-hydroxyethyl methacrylate reacted with anhydride group and alcohol in addition to this Than for 0.1/0.9.Then, stop being blown into air into liquid phase, exist about 90 DEG C while flowing into nitrogen into gas phase and continue to stir It mixes, it is small with about 4 as the compound (c) selected from one or more of (methyl) acrylate, (methyl) acrylic acid and styrene When instill 214 parts of methyl methacrylate, 222 parts of cyclohexyl methacrylate, 10 parts of styrene, ethyleneglycol dimethacrylate 5 parts of 2 parts of ester, 2 parts of acrylic acid and Perbutyl PV, 189.5 parts of toluene, 63 parts of butyl acetate mixed liquor, then with about 1 Hour instills the mixed liquor of 5 parts of Perbutyl PV, 70 parts of toluene, continues stir about 1 hour, then cools to room temperature, obtain Polymer composition (P-24) containing modified chlorinated polyolefin.The obtained polymer composition containing modified chlorinated polyolefin (P-24) solid component is about 46%, and the hydroxyl value of resin solid content is about 9mgKOH/g.In addition, the chlorination in composition is poly- The ingredient ratio of olefin skeletal and acrylic resin skeleton is about 10/90.
The manufacture of coating composition
Embodiment 19
By 100 parts of the polymer composition (P-1) and " ス ミ ジ obtained in embodiment 1 containing modified chlorinated polyolefin (trade name firmly changes U ベ ス ト ロ ウ レ タ Application society system, the chlorinated isocyanurates of hexamethylene diisocyanate to ュ ー Le N3300 " Body, solid component containing ratio 100%, isocyanate content 21.6wt%) 3.2 parts it is mixed uniformly with being combined into middle addition conduct 0.15 part of the dibutyl tin dilaurate of catalyst further adds toluene and butyl acetate, adjusts viscosity, obtain 20 DEG C with The coating composition No.1 that the viscosity of Ford cup No.4 measurement is about 30 seconds.It is explained, it is above-mentioned " ス ミ ジ ュ ー Le N3300 " In isocyanate group and the above-mentioned polymer composition (P-1) containing modified chlorinated polyolefin resin component in hydroxyl Equivalent proportion (NCO/OH) is about 1.8.
Embodiment 20~36 and comparative example 7~12
In embodiment 19, the proportion of polymer composition and polyisocyanate compound containing modified chlorinated polyolefin Form shown in table 1 as be described hereinafter, in addition to this, operate similarly to Example 19, obtain 20 DEG C with Ford cup No.4 measurement Each coating composition No.2~24 that viscosity is 30 seconds.In addition, changing since comparative example 7~9 could not be manufactured as containing for raw material Property chloridized polyolefin polymer composition (" P-19 "~" P-21 "), because without manufacture coating composition.
To each coating composition obtained above, evaluated by following test methods.By evaluation result and coating It forms shown in table 1 together.
[table 1]
Table 1
Test method
Manufacture stability: the case where will manufacturing the polymer composition containing modified chlorinated polyolefin, is evaluated as "○", it is impossible to which the case where manufacturing is evaluated as "×".
Curability (gel fraction (gel content)): being coated with each coating composition to dry film thickness on a glass is 40 μ M, the heat drying 30 minutes at about 90 DEG C.Then, the film on the glass plate, quality measurement (Wa) are recycled.Then, by the painting Film is fitted into the mesh container of the stainless steel of 200 purposes, is mentioned while flowing back 1 hour in the acetone for being heated up to about 56 DEG C It takes, measures the film quality (Wb) at 100 DEG C after drying 1 hour, the insoluble film residual rate (matter that will be calculated according to the following formula Measure %) it is used as gel fraction, by following benchmark evaluation curability.
Gel fraction (quality %)=(Wb/Wa) × 100
A: gel fraction is 70% or more
B: gel fraction is 60% more than and less than 70%
C: gel fraction is 50% more than and less than 60%
D: gel fraction is 30% more than and less than 50%
E: gel fraction is less than 30%.

Claims (8)

1. the manufacturing method of the polymer composition containing modified chlorinated polyolefin comprising with allyloxy and hydroxyl Under the coexisting of compound (a), make the chloridized polyolefin (b) with allyloxy and containing selected from (methyl) acrylate, (first Base) the polymerizable monomer copolymerization of compound (c) of one or more of acrylic acid and styrene obtains modified chlorinated polyolefin Process.
2. method described in claim 1, wherein the above-mentioned compound (a) with allyloxy and hydroxyl is the following general formula (I) The compound of expression:
In formula, R1And R2Each independently represent carbon number 2 or 3 can branch alkylidene, m, n each independently represent 0~50 The sum of real number and m and n are 1 or more real number, can be block structure or disordered structure.
3. method of any of claims 1 or 2, wherein the above-mentioned chloridized polyolefin (b) with allyloxy is by making to have Addition occurs for the compound (a) with allyloxy and hydroxyl that the chloridized polyolefin (d) of anhydride group and above-mentioned logical formula (I) indicate Obtained from reaction.
4. the described in any item methods of claims 1 to 3, wherein the above-mentioned compound (a) with allyloxy and hydroxyl is alkene Allyloxyethanol.
5. the polymer composition containing modified chlorinated polyolefin is by the compound with allyloxy and hydroxyl (a) under coexisting, make the chloridized polyolefin (b) with allyloxy and containing selected from (methyl) acrylate, (methyl) propylene Obtained from polymerizable monomer copolymerization of the acid with the compound (c) of one or more of styrene.
6. solidification compound has reactive crosslinking containing the polymer composition described in claim 5 and with hydroxyl Agent.
7. coating composition contains the polymer composition described in claim 5.
8. coating composition as claimed in claim 7, also containing has reactive crosslinking agent with hydroxyl.
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