CN102574958B - Novel vinylidene fluoride copolymers and processes for production thereof - Google Patents
Novel vinylidene fluoride copolymers and processes for production thereof Download PDFInfo
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- CN102574958B CN102574958B CN201080045460.6A CN201080045460A CN102574958B CN 102574958 B CN102574958 B CN 102574958B CN 201080045460 A CN201080045460 A CN 201080045460A CN 102574958 B CN102574958 B CN 102574958B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F214/18—Monomers containing fluorine
- C08F214/22—Vinylidene fluoride
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F214/18—Monomers containing fluorine
- C08F214/20—Vinyl fluoride
- C08F214/205—Vinyl fluoride with non-fluorinated comonomers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/12—Hydrolysis
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
- C08F2800/10—Copolymer characterised by the proportions of the comonomers expressed as molar percentages
Abstract
A vinylidene fluoride copolymer which comprises 99.9 to 90mol% of vinylidene fluoride monomer units, 0.1 to 10mol% of methylidenemalonic ester monomer units, and 0 to 10mol% of other monomer units and which has a weight-average molecular weight of 200,000 or more; a vinylidene fluoride copolymer as described above, which is modified by hydrolyzing 10 to 90% of the total number of the ester groups of the methylidenemalonic ester monomer units; and processes for the production of the copolymers.
Description
Technical field
The present invention relates to thermotolerance, weathering resistance, chemical resistant properties, stain resistance excellence, cementability is good, the vinylidene fluoride multipolymer that painted when forming process reduced and the manufacture method of this vinylidene fluoride multipolymer.The vinylidene fluoride multipolymer being obtained by the present invention is useful in the fields such as various forming process product, tackiness agent, coating.
Background technology
By excellences such as the chemical resistant properties of the poly-vinylidene fluoride resin of vinylidene fluoride cell formation, weathering resistance, stain resistances, and can be with acting on the material of being manufactured various films, products formed by melt molding.In addition, can also be used as coating, tackiness agent, but because the bonding strength of the base materials such as poly-vinylidene fluoride resin and metal is little, therefore expect the improvement of bonding strength.
In the past, in order to improve the bonding strength of poly-vinylidene fluoride resin, vinylidene fluoride (following, to be sometimes referred to as " VDF ") can be carried out to copolymerization with other monomer.
Generally speaking, free-radical polymerized about vinyl monomer, advocates the Q-e theory of predicting the copolyreaction in the radical polymerization of this monomer by the Q value that represents resonance effect of vinyl monomer and the e value that represents polarity effect.By with reference to this Q-e theory, can predict to a certain extent the copolymerizable of 2 kinds of different monomers.(compile with reference to polymer association, " new edition polymer dictionary ", first edition, towards storehouse bookstore, on November 25th, 1988, p.99 (non-patent literature 1) etc.)
But about the copolymerizable of vinylidene fluoride and other vinyl monomer, due to the hydrogen of vinylidene fluoride free polymer readical, to capture ability strong, and the extremely high singularity of the e value of vinylidene fluoride, is therefore difficult to predict with reference to Q-e theory.In addition, about the copolymerizable of vinylidene fluoride, be difficult to fully carry out investigation, the research of system, the report example of the multipolymer of vinylidene fluoride limits.As 1, the multipolymer of 1-difluoroethylene, the multipolymer of the fluorochemical monomers such as known and R 1216, trifluorochloroethylene, and become commercialized and (compile with reference to inner river filial piety minister, " ふ つ element Trees fat Ha Application De Block Star Network (fluoro-resin handbook) ", first edition, Nikkan Kogyo Shimbun, November 30 nineteen ninety, p.363 (non-patent literature 2) etc.), but they not necessarily point to the improvement of cementability, therefore, also expect the improvement of cementability.
Therefore, in Japanese kokai publication sho 56-133309 communique (patent documentation 1), show following treatment process: by irradiating poly-1 of ionizing radiation, graft polymerization acrylic monomer on the skeleton of 1-difluoroethylene, thereby poly-vinylidene fluoride can directly be bonded in metallic surface without vehicles such as caking agents.But, owing to will carrying out the ionizing irradiation of radioactive rays in the method, therefore need large-scale equipment.
In Japanese kokai publication hei 2-604 communique (patent documentation 2), show, by 1, in the multipolymer of 40～95 % by mole of 1-difluoroethylenes and 5～60 % by mole of maleic anhydrides, use alcohol or water to make anhydride moiety 90～100% open loops, thus make the solvent solubility of multipolymer and bridging property good.
In addition, in Japanese kokai publication hei 6-172452 communique (patent documentation 3), show a kind of improvement and 1 of the bonding force of metal etc., chemical resistant properties excellence, 1-fluoride copolymers, its be monoesters 0.1～3 weight part of the unsaturated dibasic acids such as monomer 100 weight parts that contain the above vinylidene fluoride of 80 % by weight and monomethyl maleate, ethyl maleate is carried out to copolymerization and.
But these have the thermotolerance defectiveness of the vinylidene fluoride multipolymer of ester or its modification body, in melt molding, have products formed painted and make commodity value reduce problem, therefore expect the improvement of coloring resistance.
Prior art document
Patent documentation
Patent documentation 1: Japanese kokai publication sho 56-133309 communique (UK Patent Application discloses No. 2072203)
Patent documentation 2: Japanese kokai publication hei 2-604 communique
Patent documentation 3: Japanese kokai publication hei 6-172452 communique (No. 5415958th, United States Patent (USP))
Non-patent literature
Non-patent literature 1: polymer association compiles, " new edition polymer dictionary ", first edition, towards storehouse bookstore, on November 25th, 1988, p.99
Non-patent literature 2: inner river filial piety minister is compiled, " ふ つ element Trees fat Ha Application De Block Star Network (fluoro-resin handbook) ", first edition, Nikkan Kogyo Shimbun, November 30 nineteen ninety, p.363
Summary of the invention
The problem that invention will solve
Main purpose of the present invention is to provide thermotolerance, weathering resistance, chemical resistant properties, stain resistance excellence, and cementability is good, the vinylidene fluoride multipolymer that painted when forming process reduced and the manufacture method of this vinylidene fluoride multipolymer.
For solving the method for problem
The inventor etc. conduct in-depth research repeatedly in order to reach above-mentioned purpose, found that, the new vinylidene fluoride multipolymer with specific ratio with vinylidene fluoride monomeric unit and methylene malonate monomeric unit can solve problem.In addition find, make its modification by the ester moiety of this vinylidene fluoride multipolymer is hydrolyzed, thereby can obtain the vinylidene fluoride multipolymer that ester moiety has been modified, this vinylidene fluoride multipolymer being modified can solve problem.
; according to the present invention; provide a kind of 1; 1-fluoride copolymers; it has 0～10 % by mole of 0.1～10 % by mole of methylene malonate monomeric unit shown in 99.9～90 % by mole of the vinylidene fluoride monomeric units shown in formula (1), formula (2) and the monomeric unit except above-mentioned monomeric unit, and weight-average molecular weight is 200; more than 000
R
1and R
2be the aliphatic alkyl of H or carbonatoms 1～5 independently of one another, wherein, R
1and R
2be except the situation of H simultaneously.
In addition,, according to the present invention, provide a kind of modification 1,1-fluoride copolymers, it is in above-mentioned vinylidene fluoride multipolymer, and 10～90% total hydrolysis of the ester group that the methylene malonate monomeric unit shown in above-mentioned formula (2) is had form.
In addition, according to the present invention, provide a kind of 1, the manufacture method of 1-fluoride copolymers, described vinylidene fluoride multipolymer has 1 shown in formula (1), 0～10 % by mole of 0.1～10 % by mole of methylene malonate monomeric unit shown in 99.9～90 % by mole of 1-difluoroethylene monomeric units, formula (2) and the monomeric unit except above-mentioned monomeric unit, and weight-average molecular weight is more than 200,000
Following monomer mixture and polymerization starter are dispersed in the aqueous medium that comprises dispersion stabilizer, be warming up to the polymerization temperature more than decomposition temperature of polymerization starter, carry out polyreaction, described monomer mixture contains 1,0.1～10 % by mole of methylene malonate shown in 99.9～90 % by mole of 1-difluoroethylenes, formula (3) and other can copolymerization 0～10 % by mole of monomer
R
1and R
2be the aliphatic alkyl of H or carbonatoms 1～5 independently of one another, wherein, R
1and R
2be except the situation of H simultaneously.
In addition, according to the present invention, a kind of modification 1 is provided, the manufacture method of 1-fluoride copolymers, it is above-mentioned 1, in the manufacture method of 1-fluoride copolymers, further use alkali metal halide or alkali metal hydroxide, total 10～90% of the ester group that the methylene malonate monomeric unit shown in above-mentioned formula (2) is had is hydrolyzed.
The effect of invention
Vinylidene fluoride multipolymer of the present invention performance provides thermotolerance, weathering resistance, chemical resistant properties, stain resistance excellence, and cementability is good, the such effect of vinylidene fluoride multipolymer that painted when forming process reduced.In addition, owing to deriving from as with 1, the functional group that the ester group of the methylene malonate that the comonomer of 1-difluoroethylene copolymerization uses is chemical reactivity, therefore of the present invention 1, the performance of 1-fluoride copolymers can be using its ester moiety as basic point, by carrying out chemical modification with reacting of various compounds, can import the such effect of required functional group to vinylidene fluoride multipolymer.
In addition, vinylidene fluoride multipolymer performance of the present invention can easily be manufactured such effect by aqueous dispersion polymerization.
Brief description of the drawings
Fig. 1 is the synthetic schemes of methylene radical dimethyl malonate.
Fig. 2 is the vinylidene fluoride multipolymer of embodiment 2
1h-NMR spectrum.
Fig. 3 is the IR spectrum of the vinylidene fluoride multipolymer of embodiment 2.
Fig. 4 is the TGA heat decomposition curve figure of embodiment 1, comparative example 1 and 2.
Fig. 5 is the vinylidene fluoride multipolymer of embodiment 5
1h-NMR spectrum.
Fig. 6 is the IR spectrum of the vinylidene fluoride multipolymer of embodiment 5.
Embodiment
1.1,1-fluoride copolymers
Of the present invention new 1,1-fluoride copolymers is for having 1 shown in above-mentioned formula (1), 0～10 % by mole of 0.1～10 % by mole of methylene malonate monomeric unit shown in 99.9～90 % by mole of 1-difluoroethylene monomeric units, formula (2) and the monomeric unit except above-mentioned monomeric unit, and weight-average molecular weight Mw is 200, more than 000 vinylidene fluoride multipolymer.Of the present invention 1, 1-fluoride copolymers is preferably has 1, 0.1～8 % by mole of 99.9～92 % by mole of 1-difluoroethylene monomeric units and methylene malonate monomeric unit, more preferably have 1, 0.2～6 % by mole of 99.8～94 % by mole of 1-difluoroethylene monomeric units and methylene malonate monomeric unit, more preferably have 1, 0.2～4 % by mole of 99.8～96 % by mole of 1-difluoroethylene monomeric units and methylene malonate monomeric unit, be particularly preferably and have 1, 1 of 0.2～1 % by mole of 99.8～99 % by mole of 1-difluoroethylene monomeric units and methylene malonate monomeric unit, 1-fluoride copolymers.If 1,1-difluoroethylene monomeric unit exceedes 99.9 % by mole, close to 1, the homopolymer of 1-difluoroethylene, therefore bad with the cementability of metal etc., on the other hand, if 1,1-difluoroethylene monomeric unit is lower than 90 % by mole, and thermotolerance, chemical resistant properties are insufficient, sometimes in the time of forming process, occur painted.
Of the present invention 1,1-fluoride copolymers has above-mentioned 1,0.1～10 % by mole of 99.9～90 % by mole of 1-difluoroethylene monomeric units and above-mentioned methylene malonate monomeric unit, but can have as required except 0～10 % by mole of the monomeric unit these monomeric units (being sometimes referred to as " other monomeric unit ").In addition, their ratio is using the total of vinylidene fluoride monomeric unit, methylene malonate monomeric unit and other monomeric unit as 100 % by mole of ratios that calculate.Other monomeric unit, as described later, can be with 1 by using, the monomer of 1-difluoroethylene or methylene malonate copolymerization comes and 1,1-difluoroethylene and methylene malonate copolymerization, thus can be used as the monomeric unit of vinylidene fluoride multipolymer and be merged in.Therefore physical property, the characteristic etc. that, can consider vinylidene fluoride multipolymer selected as the monomeric unit of vinylidene fluoride multipolymer and kind, the ratio of other monomeric unit being merged in.If painted minimizing, flexibility etc. while being considered as thermotolerance, weathering resistance, chemical resistant properties, stain resistance, cementability, the forming process of object of the present invention, as 1, the monomeric unit of 1-fluoride copolymers and the ratio of other monomeric unit of being merged in is 0～10 % by mole, be preferably 0.1～7 % by mole, more preferably 0.3～5 % by mole, be particularly preferably 0.5～3 % by mole.If the ratio of other monomeric unit is lower than 0.1 % by mole, have with only by 1, same physical property, the characteristic of vinylidene fluoride multipolymer that 1-difluoroethylene monomeric unit and methylene malonate monomeric unit form, does not almost observe the effect that is incorporated to other monomeric unit.On the contrary, if the ratio of other monomeric unit exceedes 10 % by mole, likely damage target properties, the characteristic of vinylidene fluoride multipolymer of the present invention.
In addition, the weight-average molecular weight of vinylidene fluoride multipolymer of the present invention is more than 200,000, is preferably more than 250,000, more preferably more than 260,000, is particularly preferably more than 270,000.If weight-average molecular weight, lower than 200,000, can not obtain sufficient mechanical strength sometimes.The upper limit of the weight-average molecular weight of vinylidene fluoride multipolymer is not particularly limited, but is 600,000 left and right, is generally 500,000 left and right.If weight-average molecular weight exceedes 600,000, formability worsens sometimes, and the solvability in the purposes using as solution in solvent is insufficient, and in addition, polymerization time extends significantly, and productivity reduces.
The number-average molecular weight Mn of vinylidene fluoride multipolymer of the present invention is generally 90,000～300, and 000, be preferably 100,000～250,000, more preferably 110,000～200,000.If number-average molecular weight, lower than 90,000, can not obtain sufficient mechanical strength, sometimes if number-average molecular weight exceedes 300,000, formability worsens sometimes, and the solvability in the purposes using as solution in solvent is insufficient, in addition, polymerization time extends significantly, and productivity reduces.The Mw/Mn of the expression molecular weight distribution of vinylidene fluoride multipolymer of the present invention is generally 1.80～3.50, is preferably 2.00～3.00, and more preferably 2.10～2.50.If Mw/Mn exceedes 3.50, performance, the formability of forming composition etc. are had to detrimentally affect, if Mw/Mn lower than 1.80, selected difficulty, the large spherocrystal of cooling middle generation in the time of moulding of becoming of forming process condition sometimes.
In addition, the logarithmic viscosity number of vinylidene fluoride multipolymer of the present invention (making polymkeric substance 4g be dissolved in the logarithm viscosity of the solution obtaining in the DMF of 1 liter in the time of 30 DEG C) is generally 0.8～3.8dl/g.If logarithmic viscosity number is lower than 0.8dl/g, sometimes can not obtain sufficient mechanical strength, if logarithmic viscosity number exceedes 3.8dl/g, formability worsens sometimes, solvability in the purposes using as solution in solvent reduces, in addition, polymerization time extends significantly, and productivity reduces.Logarithmic viscosity number for example, according to the application target difference of vinylidene fluoride multipolymer and use range difference,, in common injection molding, extrusion molding article, be preferably 0.8～1.8dl/g left and right, more preferably 0.9～1.7dl/g left and right, is particularly preferably 0.95～1.5dl/g left and right.In addition, in the fibre products such as fishing line, be preferably 0.9～3.8dl/g left and right, more preferably 1.0～3.7dl/g left and right, is particularly preferably 1.1～3.5dl/g left and right.
Vinylidene fluoride multipolymer of the present invention has the vinylidene fluoride monomeric unit of formula (1), the methylene malonate monomeric unit of formula (2) and other monomeric unit as required.The monomer that forms the vinylidene fluoride monomeric unit of formula (1) is vinylidene fluoride, and the monomer that forms the methylene malonate monomeric unit of formula (2) is the methylene malonate shown in formula (3).
Form of the present invention 1, the monomer of other monomeric unit that 1-fluoride copolymers can have is as required except 1, the hydrocarbon system monomers such as fluorochemical monomer beyond 1-difluoroethylene, ethene, propylene etc. can be with 1, the monomer of 1-difluoroethylene or methylene malonate copolymerization is (following, be sometimes referred to as the monomer of copolymerization " can "), preferred monomer is the fluorochemical monomer except vinylidene fluoride.As concrete example, can enumerate vinyl fluoride, trifluoro-ethylene, trifluorochloroethylene, tetrafluoroethylene, R 1216, fluoroalkyl vinyl ether etc.
Of the present invention 1,1-fluoride copolymers can be any of random copolymers, segmented copolymer and graftomer, as long as show characteristic and the feature consistent with object of the present invention, just can obtain sufficient effect, but from easy to manufacture, be particularly preferably random copolymers.
2. methylene malonate
The monomer that forms the methylene malonate monomeric unit of formula (2) is the methylene malonate shown in formula (3).In formula (3), R
1and R
2be the aliphatic alkyl of H or carbonatoms 1～5 independently of one another, the diester that comprises methylene radical propanedioic acid and monoesters.R
1and R
2simultaneously for the situation of H is not included in the category of the methylene malonate shown in formula (3).As R
1and R
2, from good stability, can obtain polymkeric substance in the short period of time, be preferably methyl, ethyl and propyl group.On the other hand, if R
1or R
2for more than 6 aliphatic alkyl of carbonatoms, due to the bulky result of ester moiety, encumber 1,1-difluoroethylene free radicals etc. extend or do not occur completely to methylene malonate addition and only by 1 to the result of methylene malonate addition, polymerization time, 1-difluoroethylene carries out polymerization and obtains 1,1-difluoroethylene homopolymer etc., therefore do not have practicality.In addition, effect of the present invention not only can be obtained by methylene malonate, and also can similarly be obtained by other alkylidene group malonic esters such as ethylidene malonic ester, propylidene malonic esters.
Methylene malonate shown in formula (3) can obtain by known manufacture method itself.The inventor etc. are based on " A Versatile and Convenient Multigram Synthesis of Methylidenemalonic Acid Diesters " (" メ チ リ デ Application マ ロ Application acid ジ work ス テ Le Hiroshima く Fitness is with may the useful な マ of In Le チ グ ラ system synthetic) ": De Keyser, J-L.; De Cock, C.J.C.; Poupaert, J.H.; Dumont, P., J.Org.Chem., 1988,53, p.4859-4862), synthesize methylene radical dimethyl malonate with the scheme of Fig. 1.
(synthesizing of methylene radical dimethyl malonate)
A. intermediate is synthetic
In the 500ml there-necked flask that possesses Di Muluo cooling tube and magnetic stick, add dimethyl malonate 66.2g (0.501 mole), anthracene 89.7g (0.503 mole), paraformaldehyde 30.0g (counting 1.00 moles with formaldehyde), venus crystals (II) monohydrate 5.00g (25 mmole), acetic acid 112ml and dimethylbenzene 112ml, reflux 24 hours.By utilizing ethanol reaction to be finished to the crude product recrystallize of rear acquisition, thereby obtain the midbody compound as colourless needle crystal.Output 107g, yield 67%.
B. methylene radical dimethyl malonate is synthetic
In the 500ml there-necked flask that possesses Di Muluo cooling tube and magnetic stick, add previous midbody compound 40.0g (0.124 mole), maleic anhydride 14.6g (0.149 mole) and whiteruss 200ml, 225 DEG C of heated and stirred 1.5 hours under nitrogen atmosphere.After reaction finishes, by underpressure distillation (66-68 DEG C/10hPa), obtain the methylene radical dimethyl malonate as colorless oil.Output 12.4g, yield 69%.
The manufacture of 3.1,1-fluoride copolymers
By making at least to have closed 1, monomer mixture and polymerization starter that 0.1～10 % by mole of methylene malonate shown in 99.9～90 % by mole of 1-difluoroethylenes, formula (3) and monomer that can copolymerization are 0～10 % by mole are dispersed in the aqueous medium that comprises dispersion stabilizer, carry out polyreaction, thereby can manufacture vinylidene fluoride multipolymer of the present invention.
Polyreaction can be undertaken by suspension polymerization or letex polymerization, but from the recovery easiness grade of vinylidene fluoride multipolymer, is preferably suspension polymerization.
(1) monomer mixture
Monomer mixture is at least containing the monomer mixture of 0～10 % by mole of 0.1～10 % by mole of the methylene malonate shown in 99.9～90 % by mole of vinylidene fluorides, formula (3) and monomer that can copolymerization.
In monomer mixture 1, the ratio of 1-difluoroethylene and methylene malonate is 1, 0.1～10 % by mole of 99.9～90 % by mole of 1-difluoroethylenes and methylene malonate, be preferably 1, 0.1～8 % by mole of 99.9～92 % by mole of 1-difluoroethylenes and methylene malonate, more preferably 1, 0.2～6 % by mole of 99.8～94 % by mole of 1-difluoroethylenes and methylene malonate, more preferably 1, 0.2～4 % by mole of 99.8～96 % by mole of 1-difluoroethylenes and methylene malonate, be particularly preferably 1, 0.2～1 % by mole of 99.8～99 % by mole of 1-difluoroethylenes and methylene malonate.
In addition, be thermotolerance, weathering resistance, chemical resistant properties, stain resistance, cementability, formability, mechanical properties etc. not to be brought to dysgenic scope and for not encumbering the scope of polyreaction about the ratio of monomer that can copolymerization, comprising 1, in the monomer mixture of the methylene malonate shown in 1-difluoroethylene, formula (3) and monomer that can copolymerization, aforementioned proportion is preferably 0.1～7 % by mole, more preferably 0.3～5 % by mole, be particularly preferably 0.5～3 % by mole.In addition, their ratio is by 1, the ratio that the total of 1-difluoroethylene monomeric unit, methylene malonate monomeric unit and other monomeric unit calculates as 100 % by mole, select most suitable scope as long as consider the polymerisation reactivity of vinylidene fluoride, methylene malonate and monomer that can copolymerization.
(2) polymerization starter
As polymerization starter, preferably use 10 hours half life temperature T
10be 30 DEG C (being roughly equivalent to the critical temperature of vinylidene fluoride)～polymerization starter of 90 DEG C, can enumerate di-isopropyl peroxydicarbonate (T
10=40.5 DEG C), peroxy dicarbonate di-n-propyl ester (T
10=40.3 DEG C), tert-Butyl peroxypivalate (T
10=54.6 DEG C), according to the suitable choice for use of required polymerization temperature.In order to obtain 1 of good thermal stability, 1-fluoride copolymers, the usage quantity of preferred polymeric initiator is as far as possible few, if but very few, polymerization time is elongated terrifically, therefore be preferably the scope of 0.01～2 quality % with respect to the amount of monomer mixture, the more preferably scope of 0.05～1.5 quality %, the more preferably scope of 0.1～1.2 quality %.If polymerization starter exceedes 2 quality %, be difficult to effectively use in polyreaction, the high temperature coloring resistance of the polymkeric substance of result gained, stripping property easily worsen.
(3) dispersion stabilizer
As dispersion stabilizer, in the time carrying out letex polymerization as polyreaction, can use general fluorine is emulsifying agent.In addition, in the time carrying out suspension polymerization as polyreaction, the suspension agent conventionally using can be used in suspension polymerization, the water-soluble polymerss such as the water-soluble cellulose ethers such as partly-hydrolysed polyvinyl acetate, methylcellulose gum, hydroxy ethyl cellulose, hydroxy propyl cellulose, HYDROXY PROPYL METHYLCELLULOSE, acrylic acid polymer, gelatin can be illustrated.The usage quantity of suspension agent being generally 0.01～2 quality % with respect to the amount of monomer mixture, be preferably 0.01～1 quality %, more preferably the ratio of 0.05～0.5 quality % is used.
(4) aqueous medium
As aqueous medium, can use common ion exchanged water, distilled water or ultrapure water etc.About the usage quantity of aqueous medium, the ratio (mass ratio) of aqueous medium/monomer mixture is generally 1/1～10/1, is preferably 1.5/1～8/1 scope, and more preferably 2/1～6/1 scope, is particularly preferably 2.5/1～5/1 scope.If the ratio of aqueous medium/monomer mixture, lower than 1/1, is difficult to stir, heat extraction, particle diameter control.In addition,, if above-mentioned ratio exceedes 10/1, there are the problems such as the Efficiency Decreasing of manufacture.
In aqueous medium, can merge and use a small amount of halogenated hydrocarbon solvent.Use for example single hydrogen pentafluorodichloropropane if merged, particularly 1,1,1,2,2-five is fluoro-3,3-propylene dichloride, 1,1,2,2,3-five is fluoro-1, and 3-propylene dichloride or their mixture can reduce the usage quantity of polymerization starter.Can use with respect to aqueous medium 100 mass parts and be 10～50 mass parts, be preferably these halogenated hydrocarbon solvents of 15～40 mass parts.
(5) use of chain-transfer agent etc.
In the time manufacturing vinylidene fluoride multipolymer of the present invention by suspension polymerization, in order to regulate the molecular weight of multipolymer of gained, preferably use chain-transfer agent.As chain-transfer agent, can enumerate acetone, isopropyl acetate, ethyl acetate, diethyl carbonate, methylcarbonate, coke acetoacetic ester, propionic acid, trifluoroacetic acid, trifluoroethanol, methylal, epoxidation 1,3-butadiene, Isosorbide-5-Nitrae-bis-
alkane, beta-butyrolactone, ethylene carbonate, vinylene carbonate etc., if but consider effectively reduce molecular weight or logarithmic viscosity number and do not encumber 1, the easiness of the thermostability of 1-fluoride copolymers, the easiness of acquisition, operation, more preferably acetone, ethyl acetate, diethyl carbonate, is particularly preferably ethyl acetate, diethyl carbonate.The usage quantity of chain-transfer agent is 0.05～5 quality % with respect to monomer mixture, is preferably 0.1～3 quality %, more preferably 0.1～1 quality %, more preferably 0.15～0.5 quality %.
Oxyhydroxide or the oxide compound etc. that in addition, can mix phosphite (ester) compound, phenolic compound, Mg or Zn are as painted preventing agent, stablizer.
(6) polyreaction
Manufacturing of the present invention 1 by suspension polymerization, when 1-fluoride copolymers, make 1, 1-difluoroethylene (critical temperature Tc=30.1 DEG C, emergent pressure Pcr=4.38MPa) 99.9～90 % by mole, mixture (hereinafter referred to as " monomer mixture ") 100 mass parts that 0.1～10 % by mole of the methylene malonate of formula (3) and monomer that can copolymerization are 0～10 % by mole are dispersed in aqueous medium 100～1000 mass parts, be preferably 150～800 mass parts, more preferably 200～600 mass parts, be particularly preferably in 250～500 mass parts, be warming up to polymerization temperature, start suspension polymerization.
Polymerization temperature T (DEG C) be more than the decomposition temperature of polymerization starter, but be preferably set to the T with respect to polymerization starter
10, meet T
10-25≤T≤T
10the temperature of+25 condition, more preferably meets T
10-20≤T≤T
10the temperature of+20 condition, more preferably meets T
10-15≤T≤T
10the temperature of+15 condition.At polymerization temperature T lower than T
10in-25 situation, because the free radical formation speed being obtained by polymerization starter is slow, therefore in order to ensure the rational productivity of polymkeric substance (for example, in polymerization time 30 hours, polymer yield described later is (following, sometimes referred to as " yield ") be more than 70 % by mole), have to increase the usage quantity of polymerization starter.Consequently, do not promote the polymerization starter of polymerization and residue and residual thereof to stay in polymkeric substance, coloring resistance and low stripping property are worsened.On the other hand, at polymerization temperature T higher than T
10+ 25 (DEG C) situation under, cause in the polymerization sharply reduction of polymerization velocity midway the polymerization of having to stop halfway, the also variation of coloring resistance of vinylidene fluoride multipolymer that result forms.Think that this is because too fast except free radical formation speed, beyond the polymerization of promotion monomer mixture, the free radical side reaction such as disproportionation reaction, hydrogen abstraction reaction each other increases.
Consider the balance of the minimizing of unreacted amount of monomer and long-timeization of polymerization time, the productivity of the multipolymer of gained is carried out the finish time of suitable selective polymerization reaction.Generally speaking, if polymerization temperature is high, polymerization time is the short period of time, and on the other hand, if polymerization temperature is low, polymerization time is long-time.In the present invention, polymerization time is generally more than 1 hour, is preferably more than 3 hours, more preferably more than 5 hours, in addition, is generally in 40 hours, is preferably in 35 hours, in more preferably 30 hours, more preferably in 25 hours.The polymer yield of polymerization finish time (refers to and will contain 1,1-difluoroethylene, methylene malonate and as required use can copolymerization the monomer mixture of monomer in form the value that the ratio of the monomer of multipolymer represents with percentage) be generally more than 70 % by mole, be preferably more than 75 % by mole, more preferably more than 80 % by mole.If yield is lower than 70 % by mole, the ratio of the monomeric unit in the vinylidene fluoride multipolymer of gained is likely different from the ratio of the monomeric unit in specific vinylidene fluoride multipolymer in the present invention.Expect that yield is large, but polymerization time president Zeitigung, if the restriction that therefore consideration is manufactured etc., 95 % by mole of left and right are the upper limit, preferably taking 93 % by mole as the upper limit, conventionally taking 90 % by mole of upper limits as yield.
After completing in polyreaction, the water paste that heating contains multipolymer makes after polymerization starter inactivation, and multipolymer is filtered, dewaters, washed and be dried, thus the powder of acquisition multipolymer.The median size of the powder of the multipolymer obtaining like this (refers to (Japanese Industrial Standards according to JIS.Identical below.) K0069, while mensuration by dry type sieve method, the represented median size of 50% accumulated value (D50) in granularity cumulative distribution) be 30～250 μ m, be preferably 40～230 μ m, more preferably 50～200 μ m left and right, loose density is 0.30～0.80g/cm
3, be preferably 0.35～0.80g/cm
3, more preferably 0.37～0.75g/cm
3left and right, operability is good.
Vinylidene fluoride multipolymer of the present invention be by make vinylidene fluoride, methylene malonate and as required can copolymerization the new vinylidene fluoride multipolymer that obtains of monomer copolymerization.
Signal by observing the C=O stretching vibration that derives from methylene malonate in IR spectrum is (for example,, in methylene radical diester malonate, at 1740cm
-1near (1740 ± 10cm
-1) observe) and
1in H-NMR spectrum, observe derive from methylene malonate-COOCH
2-near the signal (for example, in methylene radical diester malonate, (3.7 ± 0.5ppm) observes 3.7ppm) of proton, the polymkeric substance of having confirmed gained is the multipolymer that comprises methylene malonate polymer unit.The vinylidene fluoride unit comprising in vinylidene fluoride multipolymer and the ratio of methylene malonate unit by
1area in H-NMR spectrum recently calculates.
The physical property of 4.1,1-fluoride copolymers and characteristic
The measuring (DSC) by means of differential scanning calorimetry and measure the fusing point (Tm) obtaining conventionally in the scope of 130～185 DEG C, preferably in the scope of 163～177 DEG C of vinylidene fluoride multipolymer of the present invention.In addition, measure the Tc (Tc obtaining.Refer to the Tc that in process of cooling, mensuration obtains) in the scope of 100～145 DEG C, preferably in the scope of 131～137 DEG C.Particularly, as vinylidene fluoride multipolymer of the present invention, can obtain fusing point in the scope of 172～176 DEG C, the multipolymer of Tc in the scope of 131～137 DEG C.In this case, fusing point, Tc all with vinylidene fluoride homopolymer equal (174 DEG C of left and right of fusing point, 136 DEG C of left and right of Tc), of the present invention 1,1-fluoride copolymers can with the equal forming process condition compacted under of vinylidene fluoride homopolymer.
Of the present invention 1,1-fluoride copolymers is characterised in that: have 1,1-difluoroethylene monomeric unit, methylene malonate monomeric unit and other monomeric unit as required, by being adjusted at 1, the kind of other monomeric unit being incorporated to as required in 1-fluoride copolymers and ratio thereof, can design according to application target physical property and the characteristic of vinylidene fluoride multipolymer.
; of the present invention 1 of the characteristic such as painted minimizing, flexibility while having thermotolerance, weathering resistance, chemical resistant properties, stain resistance, cementability, forming process can be provided; 1-fluoride copolymers; particularly can provide and there is 1 of thermotolerance feature; 1 of 1-fluoride copolymers or the painted minimizing feature while thering is flexibility, moulding; the vinylidene fluoride multipolymers corresponding with object such as 1-fluoride copolymers.
For example, vinylidene fluoride multipolymer or fusing point that can to obtain as required fusing point be 130～168 DEG C of left and right, be preferably 140～167 DEG C of left and right are the vinylidene fluoride multipolymer of 178～185 DEG C of left and right.In addition, can also obtain as required the various vinylidene fluoride multipolymers that Tc is 100～120 DEG C of left and right, 125～133 DEG C of left and right or 140～145 DEG C of left and right.
Vinylidene fluoride multipolymer of the present invention possesses the coloring resistance equal with vinylidene fluoride homopolymer., measure about the method by according to ASTM D1925 the yellowness index (YI obtaining.YI is larger, represent that yellow is stronger), of the present invention 1, the YI of 1-fluoride copolymers is less than 0 (bearing), and the YI of the YI of vinylidene fluoride multipolymer of the present invention and vinylidene fluoride homopolymer poor (absolute value) is generally below 30, be preferably below 25, more preferably below 20.
In addition, vinylidene fluoride multipolymer of the present invention can possess the heat-resisting decomposability equal with vinylidene fluoride homopolymer.; about the thermolysis surplus of 300 DEG C in thermogravimetric analysis (TGA); of the present invention 1; 1-fluoride copolymers and 1; poor (absolute value) of the thermolysis weight rate of 1-difluoroethylene homopolymer can be in 0.3% conventionally; be preferably in 0.2%, more preferably in 0.1%.
In addition, vinylidene fluoride multipolymer of the present invention possesses than the cementability of vinylidene fluoride homopolymer excellence.Particularly, measuring that obtain and stripping strength Copper Foil according to JIS K6854 by 180 ° of stripping tests is the more than 1.2 times of stripping strength of vinylidene fluoride homopolymer, is preferably more than 1.4 times, more preferably more than 1.5 times.The upper limit of stripping strength is different and different with usage quantity according to the kind of methylene malonate using, but is 4.0 times of left and right, the balance of other characteristic of consideration and vinylidene fluoride multipolymer, be generally reach 3.5 times, preferably 3.0 times of left and right are useful.
The chemical modification of 5.1,1-fluoride copolymers
Vinylidene fluoride multipolymer of the present invention can be using the basic point as the ester group of the functional group of chemical reactivity as chemical reaction, by carrying out chemical modification with reacting of various compounds.As already described, the report of the existing vinylidene fluoride multipolymer that contains ester group up to now, but as mentioned above, due to thermotolerance, particularly coloring resistance defectiveness, Reaction conditions range that therefore can be applicable is narrow.Vinylidene fluoride multipolymer of the present invention is owing to having improved stable on heating result, and the restriction in the setting of reaction conditions is few, is therefore useful.
As an example of the chemical modification of carrying out from vinylidene fluoride multipolymer of the present invention, can enumerate undertaken by the hydrolysis of ester group derivative to carboxyl acid modified vinylidene fluoride multipolymer.The result of the further investigations such as the inventor is, by making of the present invention 1,1-fluoride copolymers reacts with the alkali metal halides such as lithiumbromide, lithium iodide, lithium hydroxide or Sodium Bromide or alkali metal hydroxide, make carboxylicesters become carboxy acid alkali's metal-salt, then, by carboxy acid alkali's metal-salt of gained is hydrolyzed, thereby can obtain by 1, total 10～90% of the ester group that the methylene malonate monomeric unit of 1-fluoride copolymers has is hydrolyzed the carboxyl acid modified vinylidene fluoride multipolymer forming.The ester group having at methylene malonate monomeric unit total form lower than 10% hydrolysis carboxyl acid modified 1, in 1-fluoride copolymers, the sum of the ester group that methylene malonate monomeric unit has is almost all residual, therefore physical property and the characteristic of the vinylidene fluoride multipolymer before modification almost do not change.In addition, the ester group having at methylene malonate monomeric unit total exceedes in the carboxyl acid modified vinylidene fluoride multipolymer that 90% hydrolysis forms, and owing to needing for a long time in order to carry out modified-reaction, therefore practicality is low.Therefore,, as long as the ratio of the material that the hydrolysis of ester group that methylene malonate monomeric unit has forms is in 10～90% scope, just can design according to application target.For example, be 35～90% left and right by the ratio that makes the material that hydrolysis of ester group forms, be preferably 40～85% left and right, can obtain the carboxyl acid modified vinylidene fluoride multipolymer with improved in adhesion feature.
As from of the present invention 1, the chemical modification that 1-fluoride copolymers carries out, the reaction of other general carbonyl also nearly all can be applied, if the formation of the acetal that use is undertaken by addition reaction, acid amides, alcohol, react the Xiang Shuanjian that carries out derivative etc. of the present invention 1 by wittig, 1-fluoride copolymers, can obtain various functional group modification vinylidene fluoride multipolymers.
Due to 1,1-difluoroethylene is be difficult for other vinyl monomer generation copolymerization and be also difficult for the monomer of the prediction of carrying out copolymerization, therefore vinylidene fluoride multipolymer of the present invention also can be positioned the important intermediate for obtaining organo-functional group modification vinylidene fluoride multipolymer.
Use of the present invention 1, the functional group modification 1 of 1-fluoride copolymers, 1-fluoride copolymers can be manufactured the various forming process product such as the parts of film, sheet, fiber, container, office equipment and electronics by the general melt molding method such as injection molding, extrusion moulding or compressed moulding, in addition, particularly, owing to improving cementability by functional group modification, therefore can expect to be widely used in the field such as tackiness agent, coating.
Embodiment
Below, enumerate embodiment and comparative example is described more specifically the present invention, but the invention is not restricted to these embodiment.
The physical property of vinylidene fluoride multipolymer (wherein, in the situation of comparative example 1 being homopolymer) and the measuring method of characteristic of embodiment and comparative example are as described below.
(1) logarithmic viscosity number
Logarithmic viscosity number is to instigate vinylidene fluoride multipolymer 4g to be dissolved in the logarithm viscosity of the solution obtaining in the DMF (DMF) of 1 liter in the time of 30 DEG C.In polymkeric substance 80mg, add DMF20ml, 70 DEG C of heating for dissolving 2 hours, modulate test sample.Use Co., Ltd. wasteland section length of schooling Ubbelodhe type viscometer 30 DEG C of mensuration of carrying out logarithmic viscosity number.
(2) weight-average molecular weight and number-average molecular weight
Weight-average molecular weight and number-average molecular weight utilize GPC (gel permeation chromatography) to measure, and polystyrene is calculated as standard model.
Vinylidene fluoride copolymer 1 0mg is dissolved in to the test sample that modulates GPC in the LiBr-NMP solution 10ml of concentration 10mM, uses Japan Spectroscopy Corporation's GPC-900 (post processed; The Shodex KD-806M processed of Showa Denko K. K), flow velocity 1ml/ minute, measure 40 DEG C of temperature and measure.
(3) fusing point and Tc
The fusing point (Tm) of vinylidene fluoride multipolymer and Tc (Tc) are measured (DSC) by means of differential scanning calorimetry and are measured.
Use press-forming machine (Co., Ltd.'s god's rattan metal industry AYSR-5 processed), preheat after 30 seconds at 210 DEG C, keep 1 minute with pressing pressure 0.5MPa, produce compressed tablet, cut out about 10mg from compressed tablet, produce the test sample of DSC.In the mensuration of DSC, use the DSC30 processed of METTLER society, in nitrogen atmosphere, in the scope of 30～220 DEG C, heat up with cooling with the speed of 10 DEG C/min, obtain fusing point (Tm) by the endotherm peak temperature in temperature-rise period, obtain Tc (Tc) by the exothermic peak temperature in process of cooling.
(4) thermolysis loss
Determine the thermolysis loss of vinylidene fluoride multipolymer by thermogravimetric analysis (TGA).
The compressed tablet of making by the test sample of the DSC from as previous cuts out the about 20mg of sample, produce the test sample of TGA, use thermogravimetric analysis device (TGA/SDTA851 processed of METTLER TOLEDO society), in nitrogen atmosphere, heat up with the speed of 10 DEG C/min, determine the thermolysis loss of sample.
(5) nucleus magnetic resonance (NMR) spectrum
Directly use commercially available deuterated DMF as measuring solvent, carry out the mensuration of the NMR spectrum of vinylidene fluoride multipolymer with Bruker society AVANCE AC processed 400FT NMR spectrograph.
(6) infrared ray absorption (IR) spectrum
By press-forming machine (god of Co., Ltd. rattan metal industry system, AYSR-5), go out the IR spectrometry sample of vinylidene fluoride multipolymer as the about 0.05mm compacting of thickness film production.Use HORIBA (Horiba Ltd) FT-730 processed to carry out the mensuration of IR spectrum.
(7) yellowness index (YI)
By using press-forming machine (Co., Ltd.'s god's rattan metal industry AYSR-5 processed), preheat after 6 minutes at 240 DEG C, keep 2 minutes with pressing pressure 10MPa, produce the test sample of the YI of vinylidene fluoride multipolymer as the test film of 11 × 6.4 × 0.6cm.
Use the color meter processed ZE6000 of Japanese electricity Se Industrial Co., Ltd, by carry out the mensuration of YI according to the method for ASTM D1925.The value of YI is larger, represents that yellow is stronger.
(8) mensuration of stripping strength
Form as electrode, make to there is synthetic graphite (Osaka ガ ス ケ ミ Liル MCMB25-28 processed of Co., Ltd.) 96 parts, 1, each sample of the composition that 1-fluoride copolymers is 4 parts is dispersed in solvent NMP, modulate the electrode slurry of solid component concentration 63 quality %, adopt rod coater to be coated on the Cu paper tinsel of thickness 10 μ m, be dried 30 minutes at 110 DEG C, producing an appearance amount of paying is 150g/m
2one side electrode coated.
By electrode coated the one side by above-mentioned acquisition long 50mm, the wide 20mm of cutting out, in room temperature with pressing pressure 0.8t/cm
2carry out plane compacting, make test film.At electrode coated Continuous pressing device for stereo-pattern, using Cu paper tinsel as " bendability is glued material ", use tensile testing machine (the STA-1150UNIVERSAL TESTING processed MACHINE of ORIENTEC society) according to JIS K6854, carry out 180 degree stripping tests with a speed 200mm/ minute, determine stripping strength.
(polymerization)
[embodiment 1] (vinylidene fluoride/methylene radical dimethyl malonate=99/1 (mass ratio))
In the autoclave of 2 liters of inner capacitiess, add ion exchanged water 1024g, methylcellulose gum 0.6g, ethyl acetate 1.2g, 50 % by weight di-isopropyl peroxydicarbonate-Chlorofluorocarbons (CFCs) 225cb solution 8.6g, 1,1-difluoroethylene (VDF) 396g, methylene radical dimethyl malonate 4.0g, until pressure decreased, to 1.5MPa, carries out the suspension polymerization of 22 hours at 29 DEG C.After polymerization completes,, make, after polymerization starter inactivation, to filter out polymkeric substance by polymer paste thermal treatment 30 minutes at 95 DEG C, dewater and wash, be then dried 20 hours at 80 DEG C, thereby obtain polymer powder.Yield is 86%, and the logarithmic viscosity number of the polymkeric substance of gained is 1.29dl/g.
[embodiment 2～4, comparative example 1～3]
In embodiment 2～4, comparative example 1～3, except by vinylidene fluoride (VDF) and comonomer than and the kind of comonomer such change as described in Table 1, employing method is similarly to Example 1 carried out.In addition, the homopolymer that comparative example 1 is vinylidene fluoride.
In addition, about embodiment 2, as shown in Figures 2 and 3, by the polymkeric substance at gained
1in H-NMR spectrum, near 3.7ppm, observe and derive from COOCH
2the signal of R (R=H in embodiment 1,2,4, comparative example 2,3, R=Me in embodiment 3), and in IR spectrum at 1740cm
-1near observe the signal that derives from C=O stretching vibration, thereby confirmed to have obtained the multipolymer of methylene malonate.Pass through
1area Ratio in H-NMR spectrum calculates the vinylidene fluoride unit that comprises in vinylidene fluoride multipolymer and the ratio (mol ratio) of methylene malonate unit.In addition, by the ratio of measuring by oxygen flask combustion method the cl concn obtaining and calculate trifluorochloroethylene unit.
[table 1]
Annotation: *) mass ratio
*) mol ratio
(various physical property)
Various physical property and the characteristic of the polymkeric substance being obtained by embodiment 1～4 and comparative example 1～3 are summarized in table 2.
[table 2]
| Mn/10 5 | Mw/10 5 | Mn/Mw | T m(℃) | T c(℃) | Y I | |
| Embodiment 1 | 1.57 | 3.49 | 2.23 | 173 | 134 | -14.2 |
| Embodiment 2 | 1.30 | 3.12 | 2.41 | 174 | 134 | -13.8 |
| Embodiment 3 | 1.22 | 2.87 | 2.35 | 174 | 135 | -9.3 |
| Embodiment 4 | 1.23 | 2.70 | 2.20 | 165 | 131 | -7.1 |
| Comparative example 1 | 1.58 | 3.81 | 2.40 | 174 | 136 | -27.0 |
| Comparative example 2 | 1.27 | 2.96 | 2.33 | 173 | 136 | 92.8 |
| Comparative example 3 | 1.14 | 3.02 | 2.65 | 173 | 135 | 49.0 |
Compared with the vinylidene fluoride homopolymer of the fusing point of the vinylidene fluoride multipolymer of the present invention of embodiment 1～3 and Tc and comparative example 1, only differ from 1～2 DEG C, keep substantially equal thermotolerance, forming process.In addition, there is of the present invention 1 of other monomeric unit due to embodiment 4, the fusing point of 1-fluoride copolymers is 165 DEG C, possesses the thermotolerance in practicality, and Tc is lower, be 131 DEG C, the multipolymer that therefore having obtained can be in the manufacture of high-crystallinity and high-intensity products formed, use in requiring the purposes of flexibility.
About the value of YI that shows coloring resistance, the difference of the vinylidene fluoride multipolymer of the present invention of embodiment 1～4 and the vinylidene fluoride homopolymer of comparative example 1 is little of 12.8～19.9, and is negative value, and therefore coloring resistance is also in sufficient level.
In addition, about 1 of embodiment 1,1-fluoride copolymers, as shown in the TGA heat decomposition curve of Fig. 4, even by exceeding the heating of 300 DEG C, weight reduces also little with degree ground with the homopolymer of the vinylidene fluoride of comparative example 1, there is the excellent heat resistance equal with vinylidene fluoride homopolymer.In addition, measure 1 of embodiment 1 by 180 ° of stripping tests according to JIS K6854,1-fluoride copolymers is as the stripping strength of the electrode coated and Copper Foil of tackiness agent, result is 4.14gf/mm, known with by 1 of comparative example 1, the homopolymer of 1-difluoroethylene is compared greatly (1.69 times) as the 2.45gf/mm in the situation of tackiness agent, aspect cementability, observes improvement.In addition, embodiment 4 is for having the of the present invention vinylidene fluoride multipolymer of trifluorochloroethylene as other monomer.Known to 1,1-, bis-difluoroethylenes and trifluorochloroethylene copolymerization can be reduced to crystallinity, be applicable to thus more to pay attention to compared with thermotolerance highly in the purposes etc. of flexibility.As such purposes that requires flexibility, can illustrate pipe (for example, Japanese kokai publication hei 6-73135 communique; With United States Patent (USP) the 5th, 292,816 correspondences), polymer gel electrolyte (for example, Japanese kokai publication hei 11-66949 communique).
On the other hand, although the copolymerization of comparative example 2 and 3 the vinylidene fluoride multipolymer Tm of maleic acid ester and Tc and above-mentioned homopolymer roughly equal, the value of YI show large on the occasion of, therefore coloring resistance is poor, lacks practicality.In addition, about 1 of comparative example 2,1-bis-fluoride copolymers, from the TGA heat decomposition curve of Fig. 4, if exceed 300 DEG C, the weight occurring rapidly reduces.
Of the present invention 1,1-fluoride copolymers aspect coloring resistance than other organo-functional group modification 1, the details of the reason of 1-fluoride copolymers excellence are not clear at present, but infer, be combined the configuration of the ester group in formed polymkeric substance with same carbon atom because of ester group thermotolerance is brought to important impact.
(hydrolysis reaction of ester moiety)
[embodiment 5]
In the 500ml there-necked flask that possesses magnetic stick and Di Muluo cooling tube, add DMF 125ml and lithiumbromide 1.17g, make solution.In this solution, add obtained by embodiment 2 of the present invention 1,1-bis-fluoride copolymers 5.05g, 100 DEG C of heated and stirred 9 hours.Naturally cool to after room temperature, use dilute hydrochloric acid to carry out redeposition operation to reaction soln.The solid filtering of gained gone out and divides and get, dewater and wash, being then dried 20 hours at 80 DEG C.The solid of mensuration gained
1h-NMR spectrum, result is by belonging to COOCH
3near the variation of integrated value of signal (3.7ppm), confirmed that total approximately 41% of number of ester groups in multipolymer is hydrolyzed (with reference to Fig. 5 and Fig. 6).
[table 3]
| Mn/10 5 | Mw/10 5 | Mn/Mw | Tm(℃) | Tc(℃) | |
| Embodiment 5 | 1.27 | 3.06 | 2.41 | 174 | 134 |
The physical property of the modification vinylidene fluoride multipolymer of gained is as shown in table 3, known have with the modification of embodiment 2 before equal fusing point and the Tc of vinylidene fluoride multipolymer.Therefore, infer modification vinylidene fluoride multipolymer can keep with homopolymer, the modification of vinylidene fluoride before the state of the equal excellent heat resistance of vinylidene fluoride multipolymer under carry out various chemical modifications.
Industry utilizability
Have 1 due to of the present invention, 1 of 1-difluoroethylene monomeric unit and methylene malonate monomeric unit, the thermotolerance of 1-fluoride copolymers, weathering resistance, chemical resistant properties, stain resistance excellence, cementability are good, painted minimizing when forming process, therefore can expect to be widely used in the fields such as various forming process product, tackiness agent, coating.
In addition, due to of the present invention 1, the ester group that 1-fluoride copolymers has is the functional group of chemical reactivity, therefore can carry out various chemical modifications by the basic point using this ester group as chemical reaction, therefore can expect to be applied to the solution in field and problem widely.
In addition, due to of the present invention 1,1-fluoride copolymers can not need to arrange special producing apparatus etc. and manufacture by the suspension polymerization that has adopted condition same, therefore can expect there is no the restriction of manufacturing and is applied to the solution in field and problem widely.
Claims (10)
1. one kind 1,1-fluoride copolymers, it has 1 shown in formula (1), 0～10 % by mole of 0.1～10 % by mole of methylene malonate monomeric unit shown in 99.9～90 % by mole of 1-difluoroethylene monomeric units, formula (2) and the monomeric unit except above-mentioned monomeric unit, and weight-average molecular weight is 200,000～600,000
R
1and R
2be the aliphatic alkyl of H or carbonatoms 1～5 independently of one another, wherein, R
1and R
2be except the situation of H simultaneously.
2. vinylidene fluoride multipolymer according to claim 1, its fusing point is in the scope of 163～177 DEG C.
3. vinylidene fluoride multipolymer according to claim 1, its stripping strength is the more than 1.2 times of vinylidene fluoride homopolymer without methylene malonate monomeric unit.
4. vinylidene fluoride multipolymer according to claim 1, R
1and R
2for methyl.
5. vinylidene fluoride multipolymer according to claim 1, R
1and R
2for ethyl.
6. a modification vinylidene fluoride multipolymer, it is in vinylidene fluoride multipolymer claimed in claim 1,10～90% total hydrolysis of the ester group that the methylene malonate monomeric unit shown in above-mentioned formula (2) is had form.
7. one kind 1, the manufacture method of 1-fluoride copolymers, described 1,1-fluoride copolymers has 1 shown in formula (1), 0～10 % by mole of 0.1～10 % by mole of methylene malonate monomeric unit shown in 99.9～90 % by mole of 1-difluoroethylene monomeric units, formula (2) and the monomeric unit except above-mentioned monomeric unit, and weight-average molecular weight is 200,000～600,000
Following monomer mixture and polymerization starter are dispersed in the aqueous medium that comprises dispersion stabilizer, be warming up to the polymerization temperature more than decomposition temperature of polymerization starter, carry out polyreaction, described monomer mixture contains 1,0.1～10 % by mole of methylene malonate shown in 99.9～90 % by mole of 1-difluoroethylenes, formula (3) and other can copolymerization 0～10 % by mole of monomer
R
1and R
2be the aliphatic alkyl of H or carbonatoms 1～5 independently of one another, wherein, R
1and R
2be except the situation of H simultaneously,
R
1and R
2be the aliphatic alkyl of H or carbonatoms 1～5 independently of one another, wherein, R
1and R
2be except the situation of H simultaneously.
8. the manufacture method of vinylidene fluoride multipolymer according to claim 7, described polymerization temperature is the temperature that meets following formula (4),
T
10－25≤T≤T
10+25······(4)
Wherein, T refer to polymerization temperature (DEG C), T
10refer to polymerization starter 10 hours half life temperatures (DEG C).
9. the manufacture method of vinylidene fluoride multipolymer according to claim 7, polymer yield when polyreaction finishes is more than 70 % by mole.
10. a modification 1, the manufacture method of 1-fluoride copolymers, it is claimed in claim 71, in the manufacture method of 1-fluoride copolymers, further use alkali metal halide or alkali metal hydroxide, total 10～90% of the ester group that the methylene malonate monomeric unit shown in formula (2) is had is hydrolyzed.
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| JP6165036B2 (en) * | 2013-11-27 | 2017-07-19 | 株式会社クレハ | Vinylidene fluoride polymer aqueous composition and use thereof |
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| JP3121943B2 (en) * | 1992-12-02 | 2001-01-09 | 呉羽化学工業株式会社 | Vinylidene fluoride copolymer |
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- 2010-09-30 CN CN201080045460.6A patent/CN102574958B/en not_active Expired - Fee Related
- 2010-09-30 WO PCT/JP2010/067154 patent/WO2011043246A1/en active Application Filing
- 2010-09-30 KR KR1020127011862A patent/KR101385921B1/en not_active IP Right Cessation
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1455663A (en) * | 2000-07-11 | 2003-11-12 | 阿斯特拉曾尼卡有限公司 | Novel aerosol formulation containing polar fluorinated molecule |
| CN101402771A (en) * | 2007-10-05 | 2009-04-08 | 罗门哈斯公司 | Improved polymer composition |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20120066064A (en) | 2012-06-21 |
| JP5639069B2 (en) | 2014-12-10 |
| WO2011043246A1 (en) | 2011-04-14 |
| KR101385921B1 (en) | 2014-04-15 |
| JPWO2011043246A1 (en) | 2013-03-04 |
| CN102574958A (en) | 2012-07-11 |
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