JPH05301927A - Fluorocopolymer and its production - Google Patents

Abstract

PURPOSE:To obtain the subject copolymer excellent in weatherability and elongation, low in surface tack, useful for sealants, etc., by copolymerization between a fluorolefin and a monomer having many ether linkages and also carrying water-curable functional group at the terminal. CONSTITUTION:The objective copolymer 1000-50000 in number-average molecular weight and <=3 in molecular weight distribution index can be obtained by copolymerization between (A) a fluorolefin (e.g. tetrafluoroethylene) and (B) a monomer copolymerizable with the component A, having >=40 ether linkages and also carrying water-curable functional group at the terminal prepared by reaction of an alkylene oxide with a hydroxyalkylvinyl ether using, as catalyst, a multiple metal cyanide complex followed by reaction with e.g. gamma-isocyanate propylmethyl dimethoxysilane. This copolymer is made up of (1) 20-70mol% of fluorolefinbased polymerized unit and (2) 1-80mol% of another kind of polymerized unit having >=40 ether linkages and also containing side chain as water- curable functional group at the terminal.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a fluorine-containing copolymer and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, in the field of sealing materials and coating materials, it has been necessary to develop a resin which is excellent in stretchability and weather resistance and can be cured at room temperature. In addition to this, in recent years, in addition to the above, for example, even if the above-mentioned conditions are satisfied, such as a silicone resin, there is a problem of occurrence of contamination due to migration of a low molecular weight silicone oil or a plasticizer contained therein and a requirement for recoatability. Is happening.

Taking a sealing material as an example, the oil-based caulking material, which does not have elasticity, has evolved into urethane type and polysulfide type, which are elastic types, and a silicone type having good weather resistance has been developed. There is a drawback that the contamination with silicone oil is remarkable. Therefore, a modified silicone having a skeleton made of polyalkylene oxide and having a siloxane bond only at the cross-linking site has been developed, but in some cases weather resistance and the like are insufficient, and it cannot be said to be a sufficient solution.

On the other hand, a fluoroolefin-vinyl ether copolymer is known as a resin having high weather resistance and room temperature curing property, and is used as a coating composition or the like. The coating composition with the resin has excellent weather resistance,
Industrial benefits such as increasing the durability of buildings are being recognized.

However, as in the present invention, a resin having higher flexibility is desired for applications such as sealing materials, elastomers, waterproof materials, adhesives, paints for PCM, and elastic paints, which are required to have higher stretchability together with weather resistance. It is rare.
Further, from the viewpoint of workability and the like, a one-component curable material is desired.

[0006]

On the other hand, a fluorine-containing copolymer having 40 or less ether bonds in the side chain is known (JP-A-2-245005). However, this copolymer is insufficient in stretchability as a one-part curability, and when the number of ether bonds is 40 or more, tackiness remains on the surface after curing and the stain resistance is deteriorated. there were.

[0007]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and is a side having 20 to 70 mol% of polymerized units (1) based on a fluoroolefin and 40 or more ether bonds. 1 to the polymerized unit (2) containing a chain
It is contained in a proportion of 80 mol% and has a number average molecular weight of 1,000.
~ 50,000, and the molecular weight distribution (weight average molecular weight /
The number average molecular weight) is 3 or less, to provide a fluorinated copolymer.

The fluorine-containing copolymer of the present invention contains 20 to 70 mol% of the polymer unit (1) based on fluoroolefin. As the fluoroolefin, tetrafluoroethylene, trifluoroethylene, vinylidene fluoride,
A fluoroolefin having 2 to 6 carbon atoms, particularly about 2 to 4 carbon atoms, such as vinyl fluoride, hexafluoropropylene, or pentafluoroethylene is preferably used. Of these, perhaloolefins in which hydrogen is completely replaced by halogen are most preferable.

The fluorine-containing copolymer of the present invention is 40
It contains 1 to 80 mol% of polymerized units having a side chain which is a functional group having at least one ether bond and having a terminal capable of being cured by the action of water. Since the specific side chain is included, the elastic body has good elasticity, and the specific cross-linking structure can be one-component curable.

Further, when producing a polymerized unit having an ether bond, an alkali catalyst such as an alkali metal compound (alkali hydroxide) is usually used as a reaction catalyst, but as the amount of alkylene oxide added increases, Along with this, many side reactions (side reactions that generate unsaturated groups) of the alkylene oxide occur, and the degree of unsaturation also increases.

In the present invention, the alkylene oxide is converted to 4 by the production using a double metal cyanide complex as a catalyst.
Since the side reaction product can be reduced even if 0 or more are added, a copolymer having a small molecular weight distribution can be obtained, surface tackiness which causes stain adhesion can be reduced, and elongation can be reduced. It can be improved.

The side chain having 40 or more ether bonds of the fluorine-containing copolymer of the present invention is a side chain consisting only of ether bond and carbon-carbon bond, such as polypropylene glycol chain, polyethylene glycol chain, etc. It may include other bonds such as bonds. The larger the number of ether bonds in the side chain, the more elastic the elastic body.

The ether bond is usually composed of an alkylene group such as a methylene group, an ethylene group, a propylene group and a butylene group. However, a compound having a small number of carbon atoms between ether bonds has high hydrophilicity, and thus is contained. The water resistance of the fluorocopolymer or its cross-linked product may decrease, which is not preferable. In addition, those having a large number of carbon atoms between ether bonds have problems such as difficulty in synthesis and are not usually preferred. Preferably, an alkylene group having about 2 to 6 carbon atoms such as ethylene group and propylene group is adopted. The alkylene group may be one in which a part or all of hydrogen bonded to carbon is substituted with a substituent such as a halogen group such as fluorine and chlorine, an alkyl group, an aryl group and the like. The number of ether bonds is preferably 40 or more in order to obtain a one-component curable and suitable sealant having good elasticity.

Further, as described above, this specific side chain is a functional group whose end is hardened by the action of water. Such functional groups include an isocyanate group, a hydrolyzable silyl group,
Examples thereof include thiol groups.

Further, the polymerized unit containing this specific side chain is
It is contained in a ratio of 1 to 80 mol%. If the content of the polymerized units containing the specific side chain is too small, it may not be possible to obtain a good elastic body or an elastic body may not be obtained, which is not preferable. In particular, a fluorine-containing copolymer containing 5 to 30 mol% of polymerized units containing a specific side chain is preferable.

Further, the fluorocopolymer of the present invention may contain other polymer units in addition to the polymer unit based on the fluoroolefin and the polymer unit containing a specific side chain. Another polymerized unit is a polymerized unit based on a monomer that can be copolymerized with a fluoroolefin, and is a polymerized unit based on an ethylenically unsaturated compound such as vinyl-based, allyl-based, isopropenyl-based, acryloyl-based, and methacryloyl-based compounds. Is mentioned. By appropriately copolymerizing these monomers, a large number of polymer units are contained between the polymers having a specific side chain, and elasticity is more effectively exhibited, which is preferable.

The fluorine-containing copolymer preferably has a molecular weight of about 50,000 or less.
If the molecular weight is too large, it is not preferable because it has poor workability when used as an elastic paint. Particularly when used without a solvent, such as for sealants, those having a large molecular weight have extremely poor workability. In the case of a one-pack type sealant, it is preferable to employ one having a molecular weight of 30,000 or less, particularly 20,000 or less. The lower limit of the molecular weight is not particularly limited, but is usually 1,000 or more, preferably 2,000.
0 or more is adopted.

The fluorinated copolymer of the present invention can be produced by the following method. Firstly, a method of copolymerizing a fluoroolefin and a monomer which is a functional group capable of being copolymerized with a fluoroolefin and having 40 or more ether bonds and having a terminal capable of being cured by the action of water. Secondly, a polymerized unit (3) having 20 to 70 mol% of a polymerized unit (1) based on a fluoroolefin, which is copolymerizable with a fluoroolefin, has 40 or more ether bonds, and has a reactive group at the terminal. Having a fluorine-containing polymer contained at a ratio of 1 to 80 mol% and a functional group curable by the action of water,
A method of reacting a compound capable of reacting with a reactive group of a fluorine-containing polymer. Thirdly, a method of containing 20 to 70 mol% of the polymerized unit (1) based on fluororefin and 1 to 80 mol% of the polymerized unit (4) having a hydroxyl group, and subjecting the alkylene oxide to an addition reaction.

In the first method, it is copolymerizable with a fluoroolefin and has 40 or more ether bonds,
Examples of the monomer having a functional group capable of being cured by the action of moisture include a monomer having a polymerizable site composed of an ethylenically unsaturated group such as vinyl group, allyl group, acryloyl group, and methacryloyl group. Adopted. As such a monomer, a monomer having 40 or more ether bonds and having a terminal functional group capable of being cured by the action of water is adopted.

The monomer having such an ether bond can be synthesized by the following method. Hydroxyalkyl vinyl ether, hydroxyalkyl allyl ether, reaction product of acrylic acid and polyhydric alcohol, reaction product of glycidyl allyl ether and alkanolamine or phenolic compound, addition reaction of alkylene oxide to hydroxyl group-containing monomer such as allyl alcohol Method of merging, hydroxyl group,
Reacting a monomer having a reactive group such as an alkoxysilyl group, an epoxy group or an amino group with a polyether compound having a group capable of reacting with the above reactive group such as an isocyanate group, an alkoxysilyl group or a carboxylic acid group. The monomer having an ether bond obtained by the method is reacted with a compound having a functional group capable of being cured by the action of water, such as a diisocyanate compound, an isocyanate alkylsilane compound, a silyl isocyanate compound, and a mercaptoalkanoic acid. A method etc. can be illustrated.

Further, in the first method, 1 monomer each having 40 or more fluoroolefins and ether bonds and having a terminal functional group capable of being cured by the action of moisture is used.
When they are polymerized one by one, there is a high possibility of alternating copolymerization. In particular, the monomer having 40 or more ether bonds and having a terminal functional group capable of being cured by the action of water is a vinyl or allyl compound. In this case, this possibility becomes extremely high. When the alternating copolymerization is carried out, the number of other polymerized units having 40 or more ether bonds and the terminal of which is a functional group capable of being cured by the action of water becomes about one, and the polymer is good. It becomes difficult to exhibit such flexibility or elasticity.

Preferably, in addition to a monomer having 40 or more fluoroolefins and ether bonds and having a terminal functional group capable of being cured by the action of moisture, a copolymerizable comonomer with these is copolymerized. In the polymer, using the method of
It is operated such that a large number of other polymerized units are present between polymerized units having a side chain having at least 40 ether bonds and having a terminal end that is a functional group capable of being cured by the action of water.

Usually, a method of copolymerizing the latter comonomer is adopted. Here, as the comonomer, a compound having a polymerizable site such as a vinyl group, an allyl group, an isopropenyl group, an acryloyl group and a methacryloyl group is adopted. Specific examples include olefins, vinyl ethers, vinyl esters, allyl ethers, allyl esters, and acrylic acid esters. Particularly, a compound having a linear, branched or alicyclic alkyl group having about 1 to 15 carbon atoms is preferable. As such a comonomer, one in which part or all of hydrogen bonded to carbon is replaced by fluorine may be adopted.

The polymerization may be carried out by any of solution polymerization, emulsion polymerization, suspension polymerization and bulk polymerization, and a predetermined amount of the monomer is allowed to act on a polymerization initiator such as a polymerization initiator or ionizing radiation. Polymerization is carried out. Other various conditions can be generally the same as those used for solution polymerization, emulsion polymerization, bulk polymerization and the like.

In the second method, the fluorine-containing copolymer is a fluoroolefin, a reactive group-containing monomer, or a group-containing monomer that can be converted into a reactive group, and, if necessary, another copolymer. It can be synthesized by merging.
As the reactive group, a hydroxyl group, a carboxylic acid group, an amino group,
Examples thereof include active hydrogen-containing groups such as mercapto groups and acid amide groups, epoxy groups, unsaturated groups, hydrolyzable silyl groups, and active halogen-containing groups. Here, the reactive group-containing monomer includes hydroxyalkyl vinyl ether, hydroxyalkyl allyl ether, hydroxyalkyl vinyl ester, glycidyl vinyl ether, glycidyl allyl ether, aminoalkyl vinyl ether, aminoalkyl allyl ether, aminoalkyl vinyl ester, aminoalkyl. Examples include allyl ether, acrylic acid, methacrylic acid, allyl vinyl ether and the like. Examples of the group that can be converted into a reactive group include an ester group that can be hydrolyzed after polymerization.

If desired, the reactive group may be converted into another reactive group after the polymerization. For example, a hydroxyl group is reacted with a polyvalent carboxylic acid group or an anhydride thereof to be converted into a carboxylic acid group, a hydroxyl group is reacted with silyl isocyanate to be converted into a hydrolyzable silyl group, an epoxy group is an alkanolamine or Examples thereof include a method of reacting a phenolic compound to convert it into a hydroxyl group, and a method of reacting a hydroxyl group isocyanate alkylmethacrylic acid to convert into an unsaturated group. Further, in synthesizing the fluorine-containing copolymer, the same monomer as the copolymer described in the first method may be copolymerized.

In the second method, a compound having at least one ether bond and having a group capable of reacting with the reactive group of the fluorine-containing copolymer is reacted with the fluorine-containing copolymer.

According to this second method, a fluorinated copolymer having an ether bond in its side chain can be produced. In particular, when the polymerized unit having a reactive group of the fluorine-containing copolymer is one having an ether bond such as vinyl ether or allyl ether, or the reaction between the fluorine-containing copolymer and the compound having an ether bond causes an ether bond. When formed, even if the compound to be reacted is a compound having one ether bond, a fluorinated copolymer having a polymerized unit containing a side chain having two ether bonds can be obtained. When the polymerized unit having a reactive group does not have an ether bond or when an ether bond is not formed by the reaction, the compound to be reacted is a compound having at least two ether bonds to obtain the above-mentioned compound of the present invention. A fluorinated copolymer having a polymerized unit containing a side chain having at least two ether bonds can be produced. 4 as a compound to react
It is preferable to react a compound having 0 or more.

The group capable of reacting with the reactive group of the fluorine-containing copolymer can be appropriately selected depending on the kind of the reactive group of the fluorine-containing copolymer. Specifically, an isocyanate group, a hydroxyl group, a carboxylic acid group, an epoxy group, an amino group,
A hydrolyzable silyl group is exemplified. Such a compound can be usually synthesized by a method in which an alkylene oxide is subjected to addition polymerization, and then a terminal hydroxyl group is reacted with a silyl isocyanate, a polycarboxylic acid or an anhydride thereof, if necessary.

The reaction between the fluorine-containing copolymer and the compound having at least one ether bond and having a group capable of reacting with the reactive group of the fluorine-containing copolymer is carried out by reacting the reactive group of the fluorine-containing copolymer. It is desirable to react under the condition of more than one compound to be reacted per one. When the amount of the compound to be reacted is small, a cross-linked structure may be formed between the fluorine-containing copolymers, and handling thereafter may be complicated, which is not preferable.

The compounds having at least one ether bond and having a group capable of reacting with the reactive group of the fluorine-containing copolymer include vinyl ethers, allyl ethers, alkylene oxide addition polymers and alkylene oxide additions. Examples include reaction products of a polymer with a compound such as an alkanolamine, a polyvalent isocyanate compound, an isocyanate alkyl acrylate, a silyl isocyanate, and a polyvalent carboxylic acid anhydride.

A third method is to use a fluorocopolymer containing a fluoroolefin-based polymerized unit (1) in an amount of 20 to 70 mol% and a hydroxyl group-containing polymerized unit (4) in an amount of 1 to 80 mol% to obtain an alkylene. This is a method in which an oxide is subjected to an addition reaction.

Here, the fluorinated copolymer can be produced by the same method as that described in the second method.
However, it is important that the fluorine-based copolymer has a hydroxyl group. Hydroxyalkyl vinyl ether, hydroxyalkyl allyl ether, allyl alcohol, etc.
When the hydroxyl group-containing monomer is copolymerized, the hydroxyl group can be easily introduced into the fluorocopolymer. On the other hand, when a monomer having a reactive group other than a hydroxyl group such as glycidyl allyl ether and acrylic acid is copolymerized, it is necessary to convert the reactive group into a hydroxyl group. Conversion of a reactive group to a hydroxyl group can be easily achieved by reacting a compound such as an alkanolamine or a polyhydric alcohol.
The addition reaction of the alkylene oxide to the fluorine-based copolymer can be carried out by the same method as in the production of ordinary polyether compounds.

The method of introducing a functional group curable by the action of moisture is carried out by reacting a compound having a functional group curable by the action of moisture and a group capable of reacting with the reactive group of the fluorine-containing polymer. To be achieved.

Examples of the compound having a functional group that can be cured by the action of water and a group that can react with the reactive group of the fluorine-containing polymer include the following compounds. For example, hexamethylene diisocyanate, polyvalent isocyanate compounds such as toluene diisocyanate, isocyanate alkylsilane compounds such as γ-isocyanatopropylmethyldimethoxysilane, silyl isocyanate compounds such as trimethoxysilyl isocyanate, 4- Examples thereof include hydrolyzable silyl group-containing compounds such as trimethoxysilyltetrahydrophthalic anhydride and thiol group-containing compounds such as mercaptoalkanonic acid and thiodialkanoic acid.

The reaction between the fluorine-containing polymer and the above-mentioned compound is preferably carried out by reacting an excessive equivalent amount of the above-mentioned compound with the reactive group of the fluorine-containing polymer. When the amount of the above-mentioned compound to be reacted is small, gelation may occur, which is not preferable. In particular, it is preferable to react 1 mol or more of the above compound per 1 mol of the reactive group of the fluorine-containing polymer.

The production of a monomer having at least 40 ether bonds in the first method and having a functional group capable of being cured by the action of moisture at the end, has at least 40 ether bonds in the second method, Manufacture of a monomer whose terminal is a reactive group,
Alternatively, in the production of a compound having at least one ether bond and the addition reaction of alkylene oxide in the third method, it is preferable to use a complex metal cyanide complex as a catalyst.

Particularly, the number of ether bonds is 40 or more,
In the case of highly adding, it is preferable to use a double metal cyanide complex because the molecular weight distribution can be suppressed to a small value. When the molecular weight distribution is small, stable physical properties can be obtained. Further, when the complex metal cyanide compound is used, it is possible to reduce side reaction products, reduce surface tackiness that is a cause of adhesion of stains, and improve elongation. There is.

Complex metal cyanide complexes are known as catalysts for alkylene oxide addition reactions and are described, for example, in the following US patents: UPS32784
57, 3278458, 3278459, 342725
6,3427334,3427345,382950
5,3941849.

This catalyst is represented by the following formula (5), for example. M1a [M2b (CN) c] d (H2O) e (R) f (M1X) g (5) M1: Fe (II), Fe (III), Co (II), Co (III ), Cr
(II), Cr (III), etc. M2: Zn (II), Fe (II), Fe (III), Co (II), etc. R: Ether or other ligand X: Anion such as halogen a, b, c , D, e, f, g: integers depending on metal valence, coordination number, etc.

The fluorine-containing copolymer of the present invention gives a cured product having good elasticity, and thus can be preferably used as a base for sealants, elastic paints and the like.

The fluorine-containing copolymer of the present invention can be used alone as a sealant or the like.
A light stabilizer, an ultraviolet absorber, a heat stabilizer, a leveling agent, a curing catalyst and the like may be added and blended. As the filler, a reinforcing filler such as fumed silica, precipitated silica, silicic acid anhydride, hydrous silicic acid and carbon black; calcium carbonate, magnesium carbonate, diatomaceous earth, calcined clay, clay, talc, titanium oxide, bentonite, Organic bentonite, ferric oxide, zinc oxide, activated zinc white,
Fillers such as hydrogenated castor oil and shirasu balloons; fibrous fillers such as asbestos, glass fibers, and filaments can be used.

In order to obtain a cured composition having high strength with these fillers, mainly fumed silica, precipitated silica,
A fluorine-containing copolymer 10 containing a filler selected from silicic acid anhydride, silicic acid hydrate, carbon black, surface-treated fine calcium carbonate, calcined clay, clay, and activated zinc white.
When it is used in the range of 1 to 100 parts by weight with respect to 0 parts by weight, favorable results are obtained. When a cured composition having low strength and large elongation is desired, titanium oxide is mainly used,
A filler selected from calcium carbonate, magnesium carbonate, talc, ferric oxide, zinc oxide, shirasu balloon, and the like is added in an amount of 5 to 2 with respect to 100 parts by weight of the fluorocopolymer.
When used in the range of 00 parts by weight, favorable results are obtained. Of course, these fillers may be used alone or in combination of two or more.

[0044]

【Example】

Synthesis Example 1 Zn in hydroxybutyl vinyl ether (HBVE)
[Co3 (CN) 6] 2-Glyme catalyst (DMC catalyst)
Propylene oxide (PO) is reacted in the presence to give a hydroxyl value of 14.0 (mgKOH / g) and a number average molecular weight of 4,
A vinyl ether having 000 polyoxyalkylene chains was obtained.

Synthesis Example 2 HBVE was reacted with PO in the presence of a DMC catalyst to give a hydroxyl value of 9.4 (mgKOH / g) and a number average molecular weight of 6,000.
A vinyl ether having 0 polyoxyalkylene chains was obtained.

Comparative Synthesis Example 1 HBVE was reacted with PO in the presence of a DMC catalyst to give a hydroxyl value of 28.1 (mgKOH / g) and a number average molecular weight of 2,0.
A vinyl ether having a polyoxyalkylene chain of 00 was obtained.

Comparative Synthesis Example 2 HBVE was reacted with PO in the presence of a potassium hydroxide (concentration 95% product used) catalyst to give a hydroxyl value of 28.1 (mgK
OH / g), and a vinyl ether having a polyoxyalkylene chain having a number average molecular weight of 2,000 was obtained.

Synthesis Examples 3 to 5 and Comparative Synthesis Examples 3 and 4 In a pressure-resistant reactor with a stirrer made of stainless steel having an internal volume of 550 ml, 112 g of xylene, 112 g of ethanol, 1.6 g of potassium carbonate and 0.5 g of azoisobutyronitrile were added. After charging, the monomers having the composition shown in Table 1 were polymerized. Polymerization was carried out by charging monomers except chlorotrifluoroethylene (CTEE) or tetrafluoroethylene (TFE), removing residual air with liquid nitrogen, and then using CT.
Introduce FE or TFE and gradually raise the temperature to 65
After maintaining the temperature at 0 ° C. and continuing the polymerization reaction for 10 hours with stirring, the reaction was carried out by cooling the reactor with water to stop the polymerization. After cooling the reactor to room temperature, unreacted monomers were extracted and the reactor was opened. After filtering the polymer solution, the solvent was removed by an evaporator to obtain a fluorinated copolymer. Table 1 shows the hydroxyl value (mgKOH / g), number average molecular weight, molecular weight distribution, and glass transition temperature of the obtained fluorocopolymer. The reaction yield was determined from the area of GPC. Reaction yield =
100 * (total resin area-unreacted monomer area) / total resin area. The molecular weight is a value including unreacted monomers.

[0049]

[Table 1]

In Table 1, CTFE is chlorotrifluoroethylene, TFE is tetrafluoroethylene, EVE is ethyl vinyl ether, CHVE is cyclohexyl vinyl ether, and HBVE is hydroxybutyl vinyl ether.

Synthesis Example 6 A fluorine-containing copolymer having a hydroxyl value of 54 and a number average molecular weight of 3,000 (toluene solution having a solid content of 50%) was reacted with PO in the presence of a DMC catalyst to give a hydroxyl value of 9 and a number. A fluorocopolymer having a polyoxyalkylene side chain with an average molecular weight of 18,000 was obtained.

Synthesis Example 7 A fluorine-containing copolymer having a hydroxyl value of 54 and a number average molecular weight of 3,000 (a toluene solution having a solid content of 50%) was reacted with PO in the presence of a DMC catalyst to give a hydroxyl value of 6 and a number. A fluorinated copolymer having a polyoxyalkylene side chain having an average molecular weight of 22,000 was obtained.

Comparative Synthesis Example 5 A fluorine-containing copolymer having a hydroxyl value of 54 and a number average molecular weight of 3,000 (toluene solution having a solid content of 50%) was reacted with PO in the presence of a DMC catalyst to give a hydroxyl value of 18, A fluorinated copolymer having a polyoxyalkylene side chain having a number average molecular weight of 9,000 was obtained.

Example 1 200 g of the fluorine-containing copolymer of Synthesis Example 3, 7.0 g of γ-isocyanatopropylmethyldimethoxysilane and 0.02 g of dibutyltin dilaurate as a curing catalyst were added to a glass container having an internal volume of 300 ml. The mixture was stirred at room temperature under a nitrogen atmosphere for 4 hours. When the infrared absorption spectrum of the obtained fluorocopolymer was measured, the absorption peak of the isocyanate group disappeared, and it was confirmed that an absorption peak of the urethane bond had occurred, and it was confirmed that the copolymer had an alkoxysilyl group. .. Next, 1 g of dibutyltin dilaurate was added to this fluorine-containing copolymer and stored in a container purged with nitrogen gas at 50 ° C. for 20 days. When the fluidity was examined, gelation was not observed and good fluidity was exhibited. .. Also, this fluorine-containing copolymer is applied to a thickness of 1 mm, and the temperature is 20 ° C and 65%.
When it was left to stand in a standard condition room of RH, it hardened in 24 hours. Therefore, it was confirmed from this that the fluorinated copolymer has a one-pack type room temperature curability.

Example 2 To a glass container having an internal volume of 300 ml, 200 g of the fluorine-containing copolymer of Synthesis Example 4, 4.7 g of γ-isocyanatopropylmethyldimethoxysilane and 0.02 g of dibutyltin dilaurate as a curing catalyst were added, The mixture was stirred at room temperature under a nitrogen atmosphere for 4 hours. When the infrared absorption spectrum of the obtained fluorocopolymer was measured, the absorption peak of the isocyanate group disappeared, and it was confirmed that an absorption peak of the urethane bond had occurred, and it was confirmed that the copolymer had an alkoxysilyl group. .. Next, 1 g of dibutyltin dilaurate was added to this fluorine-containing copolymer and stored in a container purged with nitrogen gas at 50 ° C. for 20 days. When the fluidity was examined, gelation was not observed and good fluidity was exhibited. .. Also, this fluorine-containing copolymer is applied to a thickness of 1 mm, and the temperature is 20 ° C and 65%
When it was left to stand in a standard condition room of RH, it hardened in 24 hours. Therefore, it was confirmed from this that the fluorinated copolymer has a one-pack type room temperature curability.

Examples 3, 4 Polymers having an alkoxysilyl group in the same manner as in Example 1, except that the fluorocopolymers of Synthesis Examples 5 and 6 are used instead of the fluorocopolymer of Synthesis Example 3. Got

Example 5 A polymer having an alkoxysilyl group was obtained in the same manner as in Example 2, except that the fluorine-containing copolymer of Synthesis Example 4 was used instead of the fluorine-containing copolymer of Synthesis Example 4.

Comparative Examples 1 to 3 In Example 1, instead of the fluorine-containing copolymer of Synthesis Example 3, 200 g of the fluorine-containing copolymer of Comparative Synthesis Examples 3 to 5, 20 gamma-isocyanatopropylmethyldimethoxysilane 20.
A polymer having an alkoxysilyl group was similarly obtained except that the amount was 4 g.

Comparative Example 4 Instead of the fluorine-containing copolymer, polyoxypropylenetriol having a molecular weight of 5,000 (hydroxyl value: 33.7 mg KO)
H / g) was used to obtain 23 g of γ-isocyanatopropylmethyldimethoxysilane to obtain a polymer having an alkoxysilyl group in the same manner.

Table 2 shows the test results of breaking elongation, breaking strength, elastic modulus, surface tackiness and weather resistance of the cured products obtained in Examples 1 to 5 and Comparative Examples 1 to 4.

[0061]

[Table 2]

Test Examples 1-5, Comparative Test Examples 1-4 Polymer 100 used in Examples 1-5 and Comparative Examples 1-4
A curing catalyst, titanium oxide, calcium carbonate and a silane coupling agent as an adhesiveness and storage stability imparting agent shown in Table 3 were added to g to obtain a sealing material. The obtained sealing material was stored in a container purged with nitrogen gas at 50 ° C. for 20 days and then observed. As a result, no thickening or gelation was observed, it was in a good paste form, and as a one-liquid sealing material. It was found to have storage stability.

Next, these sealing materials were spread and spread to a thickness of 2 mm, and the films obtained by standing at 20 ° C. and 65% RH for 14 days had elongation at break (%) and breaking strength (k).
Table 3 shows the results of evaluation of g / cm2), 50% modulus, surface tackiness and weather resistance.

[0064]

[Table 3]

In each of the test examples and the comparative test example, the breaking elongation, breaking strength and elastic modulus were measured in accordance with JISK-6301, and 50% modulus and surface tackiness were obtained by using Vikumatac (manufactured by Toyo Seiki) and a load of 100 g. It was measured at. Further, the weather resistance is the surface condition after 1000 hours of sunshine weatherometer (◯ indicates good, × indicates significant surface deterioration), elongation retention rate [breaking elongation after weathering test / initial breaking elongation × 100 ( %)] Was evaluated.

[0066]

EFFECT OF THE INVENTION The fluorine-containing copolymer of the present invention provides a cured product having excellent weather resistance, excellent elongation, and low surface tackiness and stain resistance. Very useful as a base.

[Procedure amendment]

[Submission date] October 23, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Item name to be corrected] 0040

[Correction method] Change

[Correction content]

This catalyst is represented by the following formula (5), for example. M ¹ _a [M ² _b (CN) _c ] _d (H ₂ O) _e (R) _f (M ¹ X) _g ………… (5) M ¹ : Fe (II), Fe (III), Co (II), Co (III), Cr
(II), Cr (III), etc. M ² : Zn (II), Fe (II), Fe (III), Co (II), etc. R: Ether or other ligand X: Anion such as halogen a, b, c, d, e, f, g: integers depending on metal valence, coordination number, etc.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0044

[Correction method] Change

[Correction content]

[0044]

Example Synthesis Example 1 ZnO was added to hydroxybutyl vinyl ether (HBVE).
[Co ₃ (CN) ₆ ] ₂ · Glyme catalyst (DMC catalyst)
Propylene oxide (PO) is reacted in the presence to give a hydroxyl value of 14.0 (mgKOH / g) and a number average molecular weight of 4,
A vinyl ether having 000 polyoxyalkylene chains was obtained.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0061

[Correction method] Change

[Correction content]

[0061]

[Table 2]

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0063

[Correction method] Change

[Correction content]

Next, these sealing materials were spread and spread to a thickness of 2 mm, and the films obtained by standing at 20 ° C. and 65% RH for 14 days had elongation at break (%) and breaking strength (k).
Table 3 shows the results of evaluation of g / cm ² ), 50% modulus, surface tackiness and weather resistance.

[Procedure amendment]

[Submission date] April 21, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0043

[Correction method] Change

[Correction content]

In order to obtain a cured composition having high strength with these fillers, mainly fumed silica, precipitated silica,
A fluorine-containing copolymer 10 containing a filler selected from silicic acid anhydride, silicic acid hydrate, carbon black, surface-treated fine calcium carbonate, calcined clay, clay, and activated zinc white.
When it is used in the range of 1 to 200 parts by weight with respect to 0 parts by weight, favorable results are obtained. When a cured composition having low strength and large elongation is desired, titanium oxide is mainly used,
A filler selected from calcium carbonate, magnesium carbonate, talc, ferric oxide, zinc oxide, shirasu balloon and the like is used in an amount of 1 to 2 with respect to 100 parts by weight of the fluorocopolymer.
When used in the range of 00 parts by weight, favorable results are obtained. Of course, these fillers may be used alone or in combination of two or more.

Claims (3)

[Claims] 1. A polymerized unit (2) containing 20 to 70 mol% of a polymerized unit (1) based on a fluoroolefin, 40 or more ether bonds and a side chain having a terminal functional group capable of being cured by the action of water. ) At a ratio of 1 to 80 mol% and a number average molecular weight of 1,000 to 50,000,
A fluorine-containing copolymer having a molecular weight distribution (weight average molecular weight / number average molecular weight) of 3 or less. 2. The fluorine-containing copolymer according to claim 1, wherein the functional group capable of being cured by the action of water is a group selected from an isocyanate group, a hydrolyzable silyl group or a thiol group. 3. The method according to claim 1, wherein the fluoroolefin and the monomer having a functional group capable of being copolymerized with the fluoroolefin and having at least 40 ether bonds and having a terminal capable of being cured by the action of water are copolymerized. A method for producing a fluorocopolymer, which comprises using a monomer having 40 or more ether bonds produced using a complex metal cyanide complex as a catalyst.