JP2757436B2 - Fluorine-containing copolymer composition - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a fluorine-containing copolymer composition.

[Prior Art] Conventionally, in the field of sealing materials and coating materials, it has been necessary to develop resins that are excellent in elasticity, excellent in weather resistance, and can be cured at room temperature. In recent years, in addition to this, even if the above conditions are satisfied, for example, 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, Requests are also emerging.

Taking the sealing material as an example, a non-stretchable oil-based caulking material has evolved into an urethane-based or polysulfide-based elastic system, and a silicone system with better weather resistance has been developed, but contamination with low molecular weight silicone oil has been developed. There is a drawback that the properties are remarkable. Therefore, modified silicones having a skeleton of polyalkylene oxide having only a siloxane bond only at a cross-linking site have been developed. However, in some cases, weather resistance and the like are insufficient, and it is difficult to say that a sufficient solution is obtained.

On the other hand, as a resin having high weather resistance and curability at room temperature, a fluoroolefin-vinyl ether copolymer is known, and is used as a coating composition or the like.
The coating composition of the resin is excellent in weather resistance and has been recognized as having industrial benefits such as enhancing the durability of buildings.

However, resins having higher flexibility are required for applications such as sealing materials, elastomers, waterproofing materials, adhesives, paints for PCM, and elastic paints, which require higher elasticity as well as weather resistance. In addition, from the viewpoint of workability and the like, one-part curable ones are desired.

Means for Solving the Problems The present invention has been made to solve the above-mentioned problems, and has a polymerization unit (1) based on a fluoroolefin of 20 to 20.
70 mol%, containing 1 to 80 mol% of a polymer unit (2) having a side chain which is a functional group having two or more ether bonds and having a terminal which can be cured by the action of moisture. On the other hand, the total of the polymerized units (1) and (2) is 30 mol%.
Provided are a fluorinated copolymer and a fluorinated copolymer composition containing a curing catalyst in the above proportions.

The fluorinated copolymer in the present invention contains 20 to 70 mol% of a polymerized unit based on a fluoroolefin. Examples of the fluoroolefin include tetrafluoroethylene, chlorotrifluoroethylene, trifluoroethylene, vinylidene fluoride, vinyl fluoride, hexafluoropropylene, pentafluoroethylene and the like having 2 to 6 carbon atoms, particularly fluoro having about 2 to 4 carbon atoms. Olefins are preferred. Among them, perhaloolefins in which hydrogen is completely replaced by halogen are most preferred.

If the polymerization unit based on the fluoroolefin is less than 20 mol%, sufficient weather resistance will not be exhibited, and stains and the like may become remarkable in long-term use. When the polymerization unit based on the fluoroolefin is more than 70 mol%, good elasticity cannot be obtained, and adhesion to other materials cannot be obtained.
Those containing 30 to 60 mol% of a polymerized unit based on a fluoroolefin are particularly preferred.

The fluorinated copolymer in the present invention contains 1 to 80 mol% of a polymerized unit containing a side chain having a functional group which has two or more ether bonds and whose terminal is curable by the action of moisture. Since this specific side chain is contained, the elastic body can have good elasticity and can be one-component curable.

The side chain having two or more ether bonds of the fluorinated copolymer in the present invention may be a side chain consisting only of an ether bond and a carbon-carbon bond, such as a polypropylene glycol chain or a polyethylene glycol chain,
A bond containing another bond such as a urethane bond, an ester bond, or an amino bond may be used.

When the number of ether bonds in the side chain is less than 2, an elastic body having preferable elasticity cannot be obtained, and is not adopted. As the number of ether bonds in the side chain increases, an elastic body having good elasticity can be obtained. However, if the length is too long, weather resistance and stain resistance decrease, which is not preferable. Usually, 40 or less, more preferably 30 or less is employed as the number of ether bonds.

In addition, the space between the ether bonds is usually composed of an alkylene group such as a methylene group, an ethylene group, a propylene group, and a butylene group. This is not preferred because the water resistance of the coalesced or crosslinked product may be reduced. Those having a large number of carbon atoms between ether bonds have problems such as difficulty in synthesis, and are not usually preferably employed. Preferably, an alkylene group having about 2 to 6 carbon atoms, such as an ethylene group or a propylene group, is employed.

In this alkylene group, a part or all of hydrogen bonded to carbon is fluorine, a halogen atom such as chlorine, an alkyl group,
It may be substituted with a substituent such as an aryl group. In particular, in order to obtain a good elastic body, the number of ether bonds in the side chain is preferably 5 or more, and in order to obtain a material suitable for applications such as sealants, the number of ether bonds is preferably 10 or more. Adopted.

As described above, this specific side chain is a functional group whose terminal can be cured by the action of moisture. Examples of such a functional group include an isocyanate group, a hydrolyzable silyl group, and a thiol group.

Further, the polymerized unit containing the specific side chain is contained at a ratio of 1 to 80 mol%. When the content ratio of the polymerized unit containing the specific side chain is too small, a favorable elastic body is not obtained or an elastic body cannot be obtained, which is not preferable. On the other hand, if the amount is too large, the weather resistance may deteriorate or an elastic body may be difficult to obtain, which is not preferable. Fluorine-containing copolymers containing polymerized units containing specific side chains at a ratio of 5 to 30 mol% are particularly preferred.

The fluorine-containing copolymer in the present invention may contain another polymerized unit in addition to the polymerized unit based on the fluoroolefin and the polymerized unit containing a specific side chain. In this case, the total of the polymerized units based on the fluoroolefin and the polymerized units containing a specific side chain is contained in a proportion of 30 mol% or more based on all the polymerized units. If the proportion of these two types of polymerized units is too small, sufficient weather resistance,
Does not exhibit stain resistance and elasticity.

Another polymerized unit is a polymerized unit based on a monomer copolymerizable with a fluoroolefin, and includes a polymerized unit based on an ethylenically unsaturated compound such as a vinyl-based, allyl-based, acryloyl-based, and methacryloyl-based compound. When these monomers are appropriately copolymerized, a large number of polymerized units are contained between the polymerized units containing a specific side chain, which is preferable because elasticity is more effectively exhibited.

Such a fluorinated copolymer preferably has a number average molecular weight (hereinafter sometimes simply referred to as molecular weight) of about 50,000 or less. If the molecular weight is too large, the coating workability is not excellent when used as an elastic paint, which is not preferable. In particular, when used without a solvent, such as for sealants, those having a large molecular weight have extremely poor workability. When used without solvent, it is preferable to employ one having a molecular weight of 15,000 or less, particularly 10,000 or less. The lower limit of the molecular weight is not particularly limited, but is usually 1,000 or more, preferably 2,000
The above is adopted.

The fluorinated copolymer in the present invention can be produced by the method exemplified below.

Method A: A method of copolymerizing a fluoroolefin and a monomer copolymerizable with the fluoroolefin and having two or more ether bonds and having a functional group whose terminal is curable by the action of moisture.

Method B: Polymerized unit (1) based on fluoroolefin
20 to 70 mol%, containing 1 to 80 mol% of a polymer unit (3) copolymerizable with a fluoroolefin and having two or more ether bonds and having a reactive group at a terminal, On the other hand, the total of the polymerized units (1) and (3) is 30.
A method comprising reacting a fluorine-containing polymer contained in a proportion of at least mol% with a compound having a functional group curable by the action of moisture and reacting with a reactive group of the fluorine-containing polymer.

In the method A, as a monomer copolymerizable with a fluoroolefin and having two or more ether bonds and having a terminal capable of being cured by the action of moisture, a vinyl group,
A monomer having a polymerizable site composed of an ethylenically unsaturated group such as an allyl group, an acryloyl group, and a methacryloyl group is employed.

As such a monomer, those having two or more ether bonds and having a terminal whose functional group can be cured by the action of moisture are employed. Such monomers include hydroxyalkyl vinyl ethers, hydroxyalkyl allyl ethers, reactants of acrylic acid and polyhydric alcohols, reactants of glycidyl allyl ether with alkanolamines or phenolic compounds, and hydroxyl-containing monomers such as allyl alcohol. To a monomer having reactivity such as a hydroxyl group, an alkoxysilyl group, an epoxy group, or an amino group, and reacting with the above reactive group such as an isocyanate group, an alkoxysilyl group, or a carboxylic acid group. Cured by the action of water such as diisocyanate compounds, isocyanate alkylsilane compounds, silyl isocyanate compounds, and mercapto alkanoic acids on monomers having ether bonds obtained by, for example, reacting a polyether compound having a susceptible group. A method of reacting a compound having ur functional group can be exemplified.

Further, in the method A, when monomers each having a functional group capable of curing by the action of water and having two or more fluoroolefins and two or more ether bonds are polymerized one by one, there is a possibility of alternate copolymerization. In particular, when the monomer having two or more ether bonds and having a functional group whose terminal is curable by the action of moisture is a vinyl or allylic compound, this possibility is extremely high. In the case of alternating copolymerization, the number of other polymerized units existing between polymerized units having two or more ether bonds and having a functional group whose terminal is curable by the action of moisture is reduced to about one, and the polymer is a good polymer. It becomes difficult to exhibit flexibility or elasticity.

Preferably, the fluoroolefin has two ether bonds.
Two or more compounds of different types are employed for one or both of the monomers having at least one and having a terminal capable of being cured by the action of moisture. Alternatively, a method of copolymerizing a fluoroolefin, a monomer having two or more ether bonds and a terminal capable of being cured by the action of moisture and a copolymerizable monomer in addition to these monomers may be used. The operation is performed such that a large number of other polymerized units are present between polymerized units having a functional group which has two or more ether bonds and can be cured by the action of moisture in the polymer. Usually, a method of copolymerizing the latter comonomer is employed.

Here, as the comonomer, a compound having a polymerizable site such as a vinyl group, an allyl group, an acryloyl group, and a methacryloyl group is employed. Specifically, olefins,
Examples include vinyl ethers, vinyl esters, allyl ethers, allyl esters, acrylic esters, methacrylic esters, and the like. Especially carbon number 1
Compounds having about 15 linear, branched or alicyclic alkyl groups are preferred. As such a comonomer, one in which part or all of the hydrogen bonded to carbon is replaced by fluorine may be used.

In the method A, the polymerization ratio of each polymerizable monomer is 20 to 70 mol% of a fluoroolefin, a monomer having two or more ether bonds and having a terminal capable of being cured by the action of moisture. Is preferably 1 to 80 mol%, and it is preferable to control so that the fluoroolefin and the monomer having two or more ether bonds are copolymerized at a ratio of 30 mol% or more based on all the polymerized units.

Such polymerization may be performed by any of solution polymerization, emulsion polymerization, suspension polymerization, and bulk polymerization.The polymerization is carried out by reacting a predetermined amount of monomer with a polymerization initiator such as a polymerization initiator or ionizing radiation. Done. Other conditions can be generally carried out under the same conditions as those for performing solution polymerization, emulsion polymerization, suspension polymerization, bulk polymerization and the like.

In the method B, 20 to 70 mol% of a polymerized unit (1) based on a fluoroolefin, and 1 of a polymerized unit (3) copolymerizable with the fluoroolefin and having two or more ether bonds and having a reactive group at a terminal. The fluorine-containing polymer contained in an amount of about 80 mol% and the total of the polymerization unit (1) and the polymerization unit (3) is not less than 30 mol% with respect to all the polymerization units is, for example, a method exemplified below. Can be manufactured.

Method C: a method of copolymerizing a fluoroolefin and a monomer copolymerizable with the fluoroolefin and having two or more ether bonds.

Method D: Polymerized unit (1) based on fluoroolefin
20 to 70 mol%, the polymerization unit (4) having a reactive group is 1 to
A fluorine-containing copolymer which is contained in a proportion of 80 mol% and the total of the polymer units (1) and (4) is 30 mol% or more with respect to all the polymer units, and at least one ether bond And reacting a compound capable of reacting with a reactive group of the fluorine-containing copolymer.

Method E: polymerized unit (1) based on fluoroolefin
20 to 70 mol%, a polymerization unit (5) having a hydroxyl group is 1 to 80
A method in which an alkylene oxide is added to a fluorine-based copolymer which is contained in a proportion of 30 mol% with respect to all the polymer units, and the total of the polymer units (1) and (5) is 30 mol% or more with respect to all the polymer units. .

In the method C, as a monomer copolymerizable with a fluoroolefin and having two or more ether bonds, a polymerizable site composed of an ethylenically unsaturated group such as a vinyl group, an allyl group, an acryloyl group, and a methacryloyl group. Is employed. As such a monomer, one having two or more ether bonds is employed. Such a monomer having an ether bond can be synthesized by the method exemplified below.

Hydroxyalkyl vinyl ether, hydroxyalkyl allyl ether, reactant of acrylic acid and polyhydric alcohol, reactant of glycidyl allyl ether with alkanolamine or phenolic compound, addition reaction of alkylene oxide to hydroxyl group-containing monomer such as allyl alcohol How to make it.

A monomer having a reactive group such as a hydroxyl group, an alkoxysilyl group, an epoxy group, or an amino group, an isocyanate group,
A method of reacting a polyether compound having a group capable of reacting with the above reactive group such as an alkoxysilyl group and a carboxylic acid group.

In the method C, when a monomer having two or more ether bonds is polymerized one by one, the possibility of alternate copolymerization is high. This possibility is very high when the body is a vinyl or allylic compound. When the copolymerization is carried out alternately, the number of other polymerization units existing between the polymerization units having two or more ether bonds becomes about one, and it becomes difficult for the polymer to exhibit good flexibility or elasticity.

Preferably, the fluoroolefin has two ether bonds.
Two or more compounds of different types are employed for one or both of the monomers having one or more monomers. In addition, a method of copolymerizing a copolymerizable monomer with a fluoroolefin or a monomer having two or more ether bonds in addition to a monomer having two or more ether bonds may be employed. It is operated so that a large number of other polymerization units exist between the polymerization units having Usually, a method of copolymerizing the latter comonomer is employed.

Here, as the comonomer, a compound having a polymerizable site such as a vinyl group, an allyl group, an acryloyl group, and a methacryloyl group is employed. Specifically, olefins,
Examples include vinyl ethers, vinyl esters, allyl ethers, allyl esters, acrylic esters, methacrylic esters, and the like. Especially carbon number 1
Compounds having about 15 linear, branched or alicyclic alkyl groups are preferred. As such a comonomer, one in which part or all of the hydrogen bonded to carbon is replaced by fluorine may be used.

In the method C, the polymerization ratio of each polymerizable monomer is such that the fluoroolefin is 20 to 70 mol%, the monomer having two or more ether bonds is 1 to 80 mol%, and It is preferable to control so that the fluoroolefin and the monomer having two or more ether bonds are copolymerized at a ratio of 30 mol% or more.

Such polymerization may be performed by any of solution polymerization, emulsion polymerization, suspension polymerization, and bulk polymerization.The polymerization is carried out by reacting a predetermined amount of monomer with a polymerization initiator such as a polymerization initiator or ionizing radiation. Done. Other conditions can be generally carried out under the same conditions as those for performing solution polymerization, emulsion polymerization, suspension polymerization, bulk polymerization and the like.

In the method D, the fluorine-containing copolymer can be synthesized by copolymerizing a fluoroolefin, a monomer containing a reactive group or a group-containing monomer that can be converted to a reactive group, and another copolymer as required. As the reactive group, a hydroxyl group,
Examples thereof include active hydrogen-containing groups such as a carboxylic acid group, an amino group, a mercapto group, and an acid amide group, an epoxy group, an unsaturated group, a hydrolyzable silyl group, and an active halogen-containing group.

Here, as the reactive group-containing monomer, hydroxyalkyl vinyl ether, hydroxyalkyl allyl ether, glycidyl vinyl ether, glycidyl allyl ether, aminoalkyl vinyl ether, aminoalkyl allyl ether, aminoalkyl allyl ether, acrylic acid, methacrylic acid, Allyl vinyl ether is exemplified.

Examples of the group that can be converted into a reactive group include an ester group that can be hydrolyzed after polymerization. Further, the reactive group may be converted to another reactive group after polymerization, if necessary. For example, a hydroxyl group is reacted with a polyvalent carboxylic acid or an anhydride thereof to convert to a carboxylic acid group, a hydroxyl group is reacted with silyl isocyanate to convert to a hydrolyzable silyl group, an epoxy group is alkanolamine or phenol. Examples of the method include a method in which a reactive compound is reacted to convert to a hydroxyl group, a method in which isocyanate alkyl methacrylate is reacted to a hydroxyl group to convert to an unsaturated group, and the like.

In synthesizing the fluorine-containing copolymer, a monomer similar to the comonomer described in the above-mentioned method C may be copolymerized. The fluorine-containing copolymer contains 20 to 70 mol% of a polymer unit (1) based on a fluoroolefin, and 1 to 80 mol% of a polymer unit (4) having a reactive group. To the polymerized unit (1) and the polymerized unit (4) in a proportion of 30 mol% or more. If each of the polymer units is not contained in the fluorine-containing copolymer at the above ratio, it becomes difficult to produce the desired fluorine-containing copolymer.

In the method D, a compound having at least one ether bond and having a group capable of reacting with a reactive group of the fluorine-containing copolymer is reacted with the fluorine-containing copolymer. According to the method D, a fluorinated copolymer having an ether bond in a side chain can be produced. In particular, when the polymerized unit having a reactive group of the fluorine-containing copolymer contains an ether bond such as vinyl ether or allyl ether, or an ether bond is formed by a reaction between the fluorine-containing copolymer and a compound having an ether bond. Is formed, even if the compound to be reacted is a compound having one ether bond, a fluorine-containing copolymer having a polymerized unit containing a side chain having two ether bonds (that is, the above-mentioned present invention) A fluorinated copolymer) is obtained.

When the polymerized unit having a reactive group does not have an ether bond or when an ether bond is not generated by the reaction, the compound to be reacted is a compound having two or more ether bonds in the present invention. A fluorinated copolymer having a polymerized unit containing a side chain having two or more ether bonds can be produced.

As the compound to be reacted, it is preferable to react a compound having 5 or more, particularly 10 or more ether bonds. The group capable of reacting with the reactive group of the fluorine-containing copolymer can be appropriately selected depending on the type of the reactive group of the fluorine-containing copolymer.

Specific examples include an isocyanate group, a hydroxyl group, a carboxylic acid group, an epoxy group, an amino group, and a hydrolyzable silyl group. Such a compound can be usually synthesized by a method in which an alkylene oxide is subjected to addition polymerization according to a conventional method, and then, if necessary, a terminal hydroxyl group is reacted with silyl isocyanate, a polyvalent carboxylic acid or an anhydride thereof. .

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 performed per one reactive group of the fluorine-containing copolymer. It is desirable that the compound be reacted under more than one condition. If the amount of the compound to be reacted is small, a cross-linked structure may be formed between the fluorine-containing polymers, and the subsequent handling may be complicated, which is not preferable.

Examples of the compound having a group capable of reacting with the reactive group of the fluorine-containing copolymer having at least one ether bond include vinyl ethers, allyl ethers, alkylene oxide addition polymers, alkylene oxide addition polymers, Examples thereof include a reaction product with a compound such as an alkanolamine, a polyvalent isocyanate compound, an isocyanate alkyl acrylate, a silyl isocyanate, or a polycarboxylic acid anhydride.

Method E is a method in which the polymerization unit (1) based on a fluoroolefin is 20 to 70 mol%, and the polymerization unit having a hydroxyl group (5)
Alkylene oxide is added to a fluorine-based copolymer containing from 1 to 80 mol% and containing a total of 30 mol% or more of polymer units (1) and (5) based on all polymer units. It is a method of reacting.

Here, the fluorine-based copolymer can be produced by a method similar to the method described in Method D described above. However, it is important that the fluorine-based copolymer has a hydroxyl group. When a hydroxyl group-containing monomer such as hydroxyalkyl vinyl ether, hydroxyalkyl allyl ether, or allyl alcohol is copolymerized, the hydroxyl group can be easily introduced into the fluorine-based copolymer.

On the other hand, glycidyl allyl ether, acrylic acid, etc.
When a monomer having a reactivity other than a hydroxyl group 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 fluorocopolymer can be carried out in the same manner as in the production of ordinary polyether compounds.

Further, the method of introducing a functional group curable by the action of moisture is achieved by reacting a compound having a functional group curable by the action of moisture and a group capable of reacting with a reactive group of a fluorine-containing polymer. .

Here, examples of the compound having a functional group curable by the action of moisture and a group capable of reacting with a reactive group of the fluorine-containing polymer include the following compounds.

Polyvalent isocyanate compounds such as hexamethylene diisocyanate and toluene diisocyanate; isocyanate alkylsilane compounds such as γ-isocyanatopropylmethyldimethoxysilane; silyl isocyanate compounds such as trimethoxysilyl isocyanate; 4-trimethoxysilyl Hydrolyzable silyl group-containing compounds such as tetrahydrophthalic anhydride, and thiol group-containing compounds such as mercaptoalkanoic acid and thiodialkanoic acid.

In the reaction between the fluorine-containing polymer and the compound, it is preferable to react the compound in an excessive amount with respect to the reactive group of the fluorine-containing polymer. If the amount of the compound to be reacted is small, gelation may occur, which is not preferable. In particular, per mole of reactive groups of the fluorine-containing polymer,
It is preferable to react 1 mol or more of the above compound.

The fluorine-containing copolymer in the present invention can be preferably used as a base for sealants, elastic paints, etc., in order to give a cured product having good elasticity.

Further, the fluorinated copolymer in the present invention can be used alone or as a sealant or the like, but a filler, a solvent, a light stabilizer, an ultraviolet absorber, a heat stabilizer, a leveling agent, and a curing catalyst may be added and compounded. Good.

As fillers, reinforcing fillers such as fume silker, precipitated silica, silicic anhydride, hydrous silicic acid and carbon black, calcium carbonate, magnesium carbonate, diatomaceous earth, calcined clay, clay, talc, titanium oxide, bentonite Fillers such as organic bentonite, ferric oxide, zinc oxide, activated zinc white, hydrogenated castor oil and shirasu balloon, and fibrous fillers such as asbestos, glass fibers and filaments can be used.

When it is desired to obtain a high-strength cured composition with these fillers, mainly fumed silica, precipitated silica, silicic anhydride,
Hydrous silicic acid, carbon black, surface-treated fine calcium carbonate, calcined clay, clay, and a filler selected from activated zinc white, etc., based on 100 parts by weight of the fluorinated copolymer,
When used in the range of 1 to 100 parts by weight, preferable results are obtained.

In addition, when it is desired to obtain a cured composition having a low strength and a large elongation, a filler selected from titanium oxide, calcium carbonate, magnesium carbonate, talc, ferric oxide, zinc oxide, and shikas balloon is mainly used. Fluorine-containing copolymer 100
When used in an amount of 5 to 200 parts by weight with respect to parts by weight, preferable results can be obtained.

These fillers may be used alone or in combination of two or more.

[Examples] Synthesis Examples 1 and 2 Hydroxybutyl vinyl ether (HBVE) and potassium hydroxide (concentration 95%) in the amounts shown in Table 1 were charged into a 5 L stainless steel pressure-resistant reactor equipped with a stirrer, and propylene oxide ( PO) was gradually added, and the reaction was carried out at 3 kg / cm ² and 110 ° C. for a predetermined time. The obtained liquid was purified with synthetic magnesia to obtain a vinyl ether having a polyoxypropylene chain. Table 1 shows the number of moles of PO added to each vinyl ether.

Synthesis Examples 3 and 4 In a pressure-resistant reactor with a stirrer made of stainless steel having an inner 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 charged, and monomers having the compositions shown in Table 2 were polymerized. For polymerization, after charging monomers other than chlorotrifluoroethylene (CTFE), dissolved air is removed with liquid nitrogen, then CTFE is introduced, the temperature is gradually raised, the temperature is maintained at 65 ° C, and stirring is performed. After the polymerization reaction was continued for 10 hours, the polymerization was stopped by cooling the reactor with water.

After cooling the reactor to room temperature, unreacted monomers were withdrawn and the reactor was opened. After filtering the polymer solution, the solvent was removed with an evaporator to obtain a fluorinated copolymer. Table 2 shows the hydroxyl value (KOH mg / g), number average molecular weight, and glass transition temperature of the obtained fluorine-containing copolymer.

Also, in the molecular weight measurement (using GPC) of the fluorine-containing copolymer in each of the synthesis examples, almost no peak was observed in the portion corresponding to the vinyl ether obtained in synthesis examples 1 and 2, so that the polyoxypropylene chain was It is presumed that the vinyl ether contained is copolymerized.

Synthesis Example 5 16 g of γ-isocyanatopropylmethyldimethoxysilane was added to 100 g of the vinyl ether having a polyoxypropylene chain obtained in Synthesis Example 1, and dibutyltin dilaurate was added at 0.0 g.
The mixture was reacted by stirring in the presence of 1 g at room temperature under a nitrogen atmosphere for 4 hours to obtain a vinyl ether having a methoxysilyl group-terminated polyoxypropylene chain.

Example 1 16.8 g of hexamethylene diisocyanate (hereinafter abbreviated as HDI) was placed in a glass container having a content of 300 mL, and 200 g of the fluorine-containing copolymer of Synthesis Example 3 was gradually dropped while stirring in a stream of dry nitrogen gas. After that, the reaction was continued for 24 hours, and the infrared absorption spectrum was measured.When it was confirmed that half of the peak of the HDI isocyanate group had changed to a urethane bond, the reaction was stopped by cooling, and 216.8 g of the isocyanate group was removed. Having a fluorine-containing copolymer.

Next, 0.01 g of dibutyltin dilaurate was added to the fluorinated copolymer, and after storage in a vessel purged with nitrogen at 50 ° C. for 20 days, no gelation was observed. I was The fluorocopolymer was applied in a thickness of 1 mm and left standing in a standard room at 20 ° C. and 65% RH, whereupon it was cured in 24 hours. From this, it was confirmed that this fluorinated copolymer had one-part room temperature curability.

Example 2 11.5 g of HDI was placed in a glass container having a content of 300 mL, and 200 g of the fluorinated copolymer of Synthesis Example 4 was gradually added dropwise while stirring in a stream of dry nitrogen gas. The reaction was continued for 24 hours, and the infrared absorption spectrum was measured. As a result of the measurement, it was confirmed that half of the peak of the HDI isocyanate group changed to a urethane bond, and the reaction was stopped by cooling to obtain 211.5 g of a fluorine-containing copolymer having an isocyanate group.

Next, 0.01 g of dibutyltin dilaurate was added to the fluorinated copolymer, and after storage in a vessel purged with nitrogen at 50 ° C. for 20 days, no gelation was observed. I was The fluorocopolymer was applied in a thickness of 1 mm and left standing in a standard room at 20 ° C. and 65% RH, whereupon it was cured in 24 hours. From this, it was confirmed that this fluorinated copolymer had one-part room temperature curability.

Comparative Example 1 In Example 1, 200 g of trifunctional polypropylene glycol having a molecular weight of 5000 and HDI were used instead of the fluorine-containing copolymer.
A polymer having an isocyanate group was obtained in the same manner as in 21.2 g to obtain a polymer having an isocyanate group. This polymer was also found to have one-part room temperature curability.

Example 3 200 g of the fluorinated copolymer of Synthesis Example 3, 20.4 g of γ-isocyanatopropylmethyldimethoxysilane, and 0.02 g of dibutyltin dilaurate as a curing catalyst were added to a glass container having a content of 300 mL at room temperature under a nitrogen atmosphere. For 4 hours. When the infrared absorption spectrum of the obtained fluorinated copolymer was measured, the absorption peak of the isocyanate group disappeared, and it was confirmed that an absorption peak of a urethane bond was generated, and it was confirmed that the copolymer had an alkoxysilyl group. .

Next, 1 g of dibutyltin dilaurate was added to the fluorinated copolymer, and the mixture was stored at 50 ° C. for 20 days in a vessel purged with nitrogen gas. When the fluidity was examined, no gelation was observed and good fluidity was exhibited. . The fluorocopolymer was applied in a thickness of 1 mm and left standing in a standard room at 20 ° C. and 65% RH, whereupon it was cured in 24 hours. From this, it was confirmed that this fluorinated copolymer had one-part room temperature curability.

Example 4 200 g of the fluorine-containing copolymer of Synthesis Example 4, 14 g of γ-isocyanatopropylmethyldimethoxysilane, and 0.02 g of dibutyltin dilaurate as a curing catalyst were added to a glass container having a content of 300 mL at room temperature under a nitrogen atmosphere. Stir for 4 hours. When the infrared absorption spectrum of the obtained fluorinated copolymer was measured, the absorption peak of the isocyanate group disappeared, and it was confirmed that an absorption peak of a urethane bond was generated, and it was confirmed that the copolymer had an alkoxysilyl group. .

Next, 1 g of dibutyltin dilaurate was added to the fluorinated copolymer, and the mixture was stored at 50 ° C. for 20 days in a vessel purged with nitrogen gas. When the fluidity was examined, no gelation was observed and good fluidity was exhibited. . The fluorocopolymer was applied in a thickness of 1 mm and left standing in a standard room at 20 ° C. and 65% RH, whereupon it was cured in 24 hours. From this, it was confirmed that this fluorinated copolymer had one-part room temperature curability.

Comparative Example 2 In Example 3, instead of the fluorinated copolymer, 200 g of trifunctional polypropylene glycol having a molecular weight of 5000 and γ-
A polymer having a methoxysilyl group was obtained in the same manner except that 23 g of isocyanatopropylmethyldimethoxysilane was used. This polymer was also found to have one-part room temperature curability.

Example 5 200 g of the fluorine-containing copolymer having an isocyanate group of Example 1 was placed in a glass container having a content of 300 mL, and 18 g of γ-aminopropyltrimethoxysilane was gradually added dropwise while stirring in a stream of dry nitrogen gas. The reaction was continued for 8 hours, and the infrared absorption spectrum was measured. As a result, it was confirmed that the peak represented by the isocyanate group disappeared and the urea bond was changed, and a fluorine-containing copolymer having an alkoxysilyl group was obtained.

Next, 1 g of dibutyltin dilaurate was added to the fluorinated copolymer, and after storage at 50 ° C. for 20 days in a container purged with nitrogen gas, when examined for fluidity, no gelation was observed and good fluidity was shown. I was The fluorocopolymer was applied in a thickness of 1 mm and left standing in a standard room at 20 ° C. and 65% RH, whereupon it was cured in 24 hours. From this, it was confirmed that this fluorinated copolymer had one-part room temperature curability.

Example 6 200 g of the fluorinated copolymer having an isocyanate group of Example 2 was placed in a glass container having a content of 300 mL, and 12 g of γ-aminopropyltrimethoxysilane was gradually added dropwise while stirring in a stream of dry nitrogen gas. The reaction was continued for 8 hours, and the infrared absorption spectrum was measured. As a result, it was confirmed that the peak represented by the isocyanate group disappeared and the urea bond was changed, and a fluorine-containing copolymer having an alkoxysilyl group was obtained.

Next, 1 g of dibutyltin dilaurate was added to the fluorinated copolymer, and after storage at 50 ° C. for 20 days in a container purged with nitrogen gas, when examined for fluidity, no gelation was observed and good fluidity was shown. I was The fluorocopolymer was applied in a thickness of 1 mm and left standing in a standard room at 20 ° C. and 65% RH, whereupon it was cured in 24 hours. From this, it was confirmed that this fluorinated copolymer had one-part room temperature curability.

Comparative Example 3 In Example 5, 200 g of the polymer obtained in Comparative Example 1 was replaced with 21 g of γ-aminopropylmethyldimethoxysilane in place of the fluorinated copolymer. I got This polymer was also found to have one-part room temperature curability.

Example 7 200 g of the fluorinated copolymer of Example 3 was placed in a glass container having a content of 300 mL, 0.06 g of triethylamine was added, and 27.2 g of 4-trimethoxysilyltetrahydrophthalic anhydride was gradually added at 50 ° C. in a stream of dry nitrogen gas. After dropwise addition, the reaction was continued for 5 hours, and the infrared absorption spectrum was measured. As a result, it was confirmed that the absorption peak based on the hydroxyl group had disappeared and the peak based on the carboxylic acid had occurred, and the reaction was stopped by cooling. g of a fluorinated copolymer having an alkoxysilyl group was obtained.

Next, 1 g of dibutyltin dilaurate was added to the fluorinated copolymer, and after storage at 50 ° C. for 20 days in a container purged with nitrogen gas, when examined for fluidity, no gelation was observed and good fluidity was shown. I was The fluorocopolymer was applied in a thickness of 1 mm and left standing in a standard room at 20 ° C. and 65% RH, whereupon it was cured in 24 hours. From this, it was confirmed that the fluorocopolymer had one-part room temperature curability.

Comparative Example 4 In Example 6, instead of the fluorinated copolymer, 200 g of trifunctional polypropylene glycol having a molecular weight of 5000, 4-
A polymer having an isocyanate group was obtained in the same manner, except that 32.6 g of trimethoxysilyltetrahydrophthalic anhydride was used. This polymer was also found to have one-part room temperature curability.

Example 8 200 g of the fluorinated copolymer having an isocyanate group of Example 1 was placed in a glass container having a content of 300 mL, and 5.8 g of allyl alcohol was gradually dropped while stirring at 80 ° C. in a dry nitrogen gas stream. The reaction was continued for 24 hours. When the infrared absorption spectrum of the reaction product was measured, a peak indicating an isocyanate group was not confirmed, but a peak indicating a urethane bond was confirmed.

To 100 g of the obtained fluorinated copolymer, 8 g of β, β'-dimethylcaptodiethyl ether, 0.5 g of t-butyl perbenzoate, and 0.05 g of tetramethylguanidine were added.
After stirring slowly, the mixture was allowed to stand at 60 ° C. for 16 hours. The product was confirmed to have no double bond by infrared spectroscopy.

Further, when 0.5 g of lead dioxide was added to this fluorinated copolymer and the fluidity was examined, no gelation was observed and good fluidity was shown. In addition, this fluorine-containing copolymer is 1m thick
m and cured in a standard room at 20 ° C. and 65% RH for 24 hours. From this, it was confirmed that this fluorinated copolymer had one-part room temperature curability.

Example 9 In a pressure-resistant reactor with a stirrer made of stainless steel having an inner volume of 550 mL,
After charging 112 g of xylene, 112 g of ethanol, 1.6 g of potassium carbonate and 0.5 g of azoisobutyronitrile, 194 g of the vinyl ether obtained in Synthesis Example 5, 19 g of cyclohexyl vinyl ether, and 11 g of ethyl vinyl ether, dissolved air was removed with liquid nitrogen. Then, 51 g of CTFE was introduced, the temperature was gradually raised, the temperature was maintained at 65 ° C., and the polymerization reaction was continued under stirring for 10 hours. Then, the reactor was cooled with water to terminate the polymerization. After cooling the reactor to room temperature, unreacted monomers were withdrawn and the reactor was opened. After filtering the polymer solution, the solvent was removed with an evaporator to obtain a fluorinated copolymer.

The number average molecular weight of the obtained fluorine-containing copolymer is 6,500,
The glass fiber temperature was -68 ° C. Further, in the molecular weight measurement (using GPC) of this fluorinated copolymer, almost no peak was observed in the portion corresponding to the vinyl ether obtained in Synthesis Example 5, so that vinyl ether having a polyoxypropylene chain was copolymerized. Therefore, it is estimated that the vinyl ether having a polyoxypropylene chain is copolymerized.

Test Example To 100 g of the fluorinated copolymer obtained in Examples 1 to 9 and Comparative Examples 1 to 4, a curing catalyst (dibutyltin dilaurate or lead dioxide), titanium oxide and calcium carbonate shown in Table 3 were added, and stainless steel was added. Spread 2mm thick on board, 20 ℃, 6
About the film obtained by standing at 5% RH for 14 days,
Tables 3 and 4 show the results of evaluation of elongation at break (%), strength at break (kg / cm ² ), 50% modulus, surface tackiness, and weather resistance. In both tables, the fluorinated copolymer of Example 1 is abbreviated as "actual 1", and the same applies to the others. The “ratio” in the test example number is a comparative test example.

In each test example, the breaking elongation, breaking strength, and 50% modulus were measured in accordance with JIS-K6301, and the surface tackiness was measured using a PictaMac (manufactured by Toyo Seiki) under a load of 100 g.
The weather resistance was as follows: Surface condition after 1000 hours of sunshine weather o-meter (◎: no change, ○: slight decrease in gloss, but no other problems, ×: significant surface degradation), elongation retention (Elongation at break after weathering test / Elongation at initial fracture × 100 (%)) was evaluated.

[Effect of the Invention] The fluorine-containing copolymer composition of the present invention has excellent weather resistance and gives a cured product having excellent elongation, and is therefore extremely useful as a sealant or an elastic paint base.

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Claims (2)

(57) [Claims] 1. A polymer unit (2) comprising 20 to 70 mol% of a polymer unit (1) based on a fluoroolefin, a polymer unit having a side chain having at least two ether bonds and having a functional group which can be cured by the action of moisture. ) In a proportion of 1 to 80 mol%, and a total of the polymerized units (1) and (2) in a proportion of at least 30 mol% with respect to all the polymerized units, and a curing catalyst A fluorine-containing copolymer composition comprising: 2. The fluorine-containing copolymer composition according to claim 1, wherein the functional group curable by the action of moisture is an isocyanate group, a hydrolyzable silyl group or a thiol group.