JP2661878B2 - Method for producing silicon-functional copolymer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] BACKGROUND OF THE INVENTION 1. Field of the Invention
More specifically, a side chain
Part of the silyl ester is a silicon-functional silyl ester
A silicon-functional copolymer characterized by conversion to
And a method for producing a condensation crosslinked product thereof. Like this
The obtained silicon-functional copolymer or its condensation cross-linked product is
The slowly soluble coating material as the main component is used in seawater.
Dissolves slowly, forming a strong coating, especially before dissolution
Can be [0002] 2. Description of the Related Art Conventionally, for example, it has been applied to a ship bottom or the like.
To form a coating film, which gradually dissolves in seawater.
Unleashes a fresh surface and has biological activity
Antifouling paint that releases compounds to prevent the growth of attached organisms
It is known. Such antifouling paints include (meth) a
Crylate and tributyltin (meth) acrylate
And copolymers, and a part of the monomer
Butylsilyl acrylate and triphenylsilyl acrylic
It is known to use a combination of rates (Japanese Patent Laid-Open No. 60-23 / 1985).
No. 1771). However, such copolymers
Thus, if totibutyltin is present in the molecule,
Due to its release into seawater by hydrolysis, its toxicity
There is a serious problem of polluting the ocean. [0003] As a group having a similar hydrolyzability, (meth)
(T) Triorgano introduced into the side chain of acrylic polymer
Silyl groups are known, and triorganos
Homo-copolymer of ril (meth) acrylate
-179514) in seawater,
And the above (meth) acrylate and ethylenically unsaturated
Slowly soluble bottom paint using copolymer with monomer disclosed
(See US Pat. No. 4,593,055).
See). [0004] Such triorganosilyl (meth) a
The acrylate homopolymer or copolymer is hydrolyzed
It has the advantage of not releasing toxic organotin compounds. I
However, such triorganotin and / or trio
(Meth) acrylic polymer having luganosilyl group in side chain
As a common drawback, it was synthesized by the usual polymerization method.
If the initial solubility in seawater is poor,
That is, the time change is large. Also, this species
Coatings of this type are vulnerable to sudden temperature changes,
Controls the molecular weight to a low level to provide excellent slow solubility
This is particularly noticeable when doing so. Therefore, its application range
The box indicates the area where temperature changes during use are not a problem.
Is limited to [0005] SUMMARY OF THE INVENTION The present invention addresses the above problems.
Solves the problem, has excellent slow-dissolving properties, and has a sharp
Can form a strong coating film that can withstand extreme temperature changes
Triorganosilyl (meth) acrylate based slowly soluble
Silicon functionality used as a main component of coating materials
Provided is a method for producing a copolymer and a condensation crosslinked product thereof.
The porpose is to do. [0006] Means for Solving the Problems The present inventors have set forth the above-mentioned object.
As a result of repeated research to achieve the target,
Ryl (meth) acrylate copolymerTriorganos
Lil group containing unitSome of them are transesterified
By introducing an i-functional group, the silicon functional group is condensed.
Easily introduce a crosslinked structure into the copolymer by a combination reaction
To withstand temperature changes,
In addition, it is possible to obtain a coating material with excellent
And found that the present invention was completed. That is, the silicon-functional copolymer of the present invention
The manufacturing method of (A) General formula (I): Embedded image (Where R¹Represents a hydrogen atom or a methyl group;²Is
Same or different from each other, not containing aliphatic unsaturated bonds
Monovalent hydrocarbon groups, at least one of which is
Represents a monovalent hydrocarbon group having 4 or more carbon atoms)G
Liorganosilyl group-containing unit;and (B) General formula (II): Embedded image (Where R³Represents a hydrogen atom or a methyl group, and Z represents,
CO ₂ R ⁴ Group, cyano group, chlorine atom, acetoxy group, O
R ⁵ Group or R ⁶ Selected from the group consisting of ⁴ , R ⁵
Is a substituted or unsubstituted alkyl having 1 to 8 carbon atoms
And R is ⁶ Is a monovalent cyclic group containing a nitrogen atom in the ring
is thereWhich represents a monovalent polar group or a phenyl group)
Repeat unitConsisting of triorganosilyl group-containing copolymer
To The general formula (R⁸)_aSix_4-a (Where R⁸Are the same or different monovalent hydrocarbons
X represents a hydroxyl group,OrAlkoxy group, alco
Xyalkoxy, acyloxy, ketoxime, ol
Ganoamino group, diorganaminoaminoxy group and organo
Selected from the group consisting of amide groupsRepresents a hydrolysable group,
a represents a number from 0 to 2)
And reacting the triorgano of some side chains of the unit (A)
By transesterifying the silyl group, (A)
Position, (B) unit, and (C) General formula (III): Embedded image (Where R⁷Is R¹Represents the same group as⁸, X and a
Is shown above)Silyl group-containing silicon functionality
unitTo obtain a silicon-functional copolymer consisting of
I do. The silicon-functional copolymer obtained by the present invention
Hydrolysis and condensation of the silicon functional group
You can get a bridge. [0008] Triorganosilyl group used in the present invention
The containing copolymer comprises (A) a unit represented by the general formula (I)
And (B) a copolymer comprising a unit represented by the general formula (II)
Body. In the general formula (I), R¹ And R^Two
Is as described above. Where R^Two Identical to each other
Or monovalent carbonization containing no different aliphatic unsaturated bonds
As the hydrogen group, methyl, ethyl, propyl, butyl,
Pentyl, hexyl, heptyl, octyl, nonyl, de
Alkyls such as sill, dodecyl, myristyl, and stearyl
Group; cyclopentyl, cyclohexyl, etc.
Alkyl group; condensed alicyclic ring such as norbornyl and norpinyl
Groups; 2-phenylethyl, 2-phenylpropyl and the like
Aralkyl groups; aryl groups such as phenyl and tolyl
Can be exemplified, and among these, excellent slow solubility and
To impart excellent properties to the coating before hydrolysis,
And hexyl and norbornyl are preferred.
In addition, R^TwoThat two of them are methyl groups
Triorganosilyl (meth) acrylate
This is advantageous for the production. The above R^Two Among which are silicon-functional copolymers
Or to impart a moderate slow solubility to the condensation cross-linked product
Is a monovalent hydrocarbon group having at least one carbon atom of 4 or more
It is necessary to be. (A) As a monomer for forming a unit
Is dimethylbutylsilyl acrylate, dimethylhexyl
Silsilyl acrylate, dimethyl octyl silyl acrylate
Relate, dimethyldecylsilyl acrylate, dimethyl
Ludodecylsilyl acrylate, dimethylcyclohexyl
Lucylyl acrylate, dimethylnorbornylsilylua
Acrylate, dimethylphenylsilyl acrylate,
Tildibutylsilyl acrylate, ethyldibutylsilyl
Acrylate, dibutylhexylsilyl acrylate
G, dibutylphenylsilyl acrylate, tributyl
Silyl acrylate, triphenylsilyl acrylate
And methacrylates corresponding to these.
Can be. Triorganosilyl (meth) acryl
Easy synthesis and moderately slow dissolution
Do not improve the physical properties of the coating before hydrolysis or hydrolysis.
From dimethylhexylsilyl acrylate, dimethyl
Renorbornylsilyl acrylate, tributylsilyl
Acrylates and their corresponding methacrylates
preferable. The unit (B) is represented by the general formula (II)Anti
UnitIt is. R in the formula³And Z are defined above
It is. In the definition of Z1Valency polarityGroup is, Synthesis
Ease, physical properties of the coating and adhesion to the application object
From,CO₂R⁴Group, cyano group, chlorine atom, acetoxy
Shi group, OR⁵Group or R⁶BaseSelected from the group consisting of.
Where R⁴, R⁵Is substituted with 1 to 8 carbon atoms or
It is an unsubstituted alkyl group. Where R⁴As a meth
, Ethyl, propyl, butyl, pentyl, hexyl,
Heptyl, octyl, 2-hydroxyethyl, 2-hydr
Examples include roxypropyl, dimethylaminoethyl and the like.
be able to. Also, when improving the hydrophilicity of the coating film
Is the R of some (B) units used⁴Is 2-hydroxy
It can also be ethyl or 2-hydroxypropyl.
R⁵Include methyl, ethyl, propyl, butyl,
Methyl, hexyl, heptyl, octyl, 2-methoxy
Ethyl, 2-ethoxyethyl and the like can be exemplified.
You. R⁶Is a monovalent cyclic group containing a nitrogen atom in the ring,
Examples thereof include pyrrolidyl and pyridyl. Forming such a unit (B)Out for
Used as a substanceMonomers include (meth)
Ril typeCompoundAnd vinyl compounds can be used
You. As the (meth) acrylic compound, methyl
Acrylate, ethyl acrylate, butyl acryle
Hexyl acrylate, octyl acrylate,
2-hydroxyethyl acrylate, 2-hydroxyp
Propyl acrylate, acrylonitrile, etc. and these
Can be exemplified.
Vinyl compounds include vinyl acetate, vinyl chloride,
Tylene, vinyl methyl ether, vinyl ethyl ether
, Vinyl propyl ether, vinyl isobutyl ether
And vinylpyrrolidone. In the triorganosilyl group-containing copolymer
The content of the (A) unit and the (B) unit is determined by the silicon content described later.
Preferred units (A) and (B) in the functional copolymer
The amount which can satisfy the new amount is preferable. That is, (A)
The content of the unit is 10 to 90 mol% in the copolymer, and
20 to 50 mol% by transesterification
(C) The sum with the amount to be converted into a unit is preferable, and (B)
Is preferably 10 to 90 mol% in the copolymer.
And more preferably 30 to 80 mol%. In the production method of the present invention,
The triorganosilyl group-containing copolymer used is, for example,
Can be manufactured by the following method. That is, (A)
And (B) polymerizing the monomer forming the unit,
(A) and (B) units having a desired average degree of polymerization
The copolymer is produced. The polymerization reaction is, for example, a suitable
Chain transfer agent and polymerization initiation as needed in organic solvent
In the presence of the agent, the polymerization is carried out at an appropriate temperature. This place
In order to obtain a copolymer having a desired average degree of polymerization,
Preferably, a transfer agent is used. The organic solvent controls the polymerization reaction and
It is used to prevent the formation of gel inside. Said yes
Solvents such as benzene, toluene and xylene
Hydrocarbon solvents: Esthetics such as ethyl acetate and butyl acetate
Solvents such as isopropanol and butanol
Solvents and dimethylformamide, dimethyl sulf
Examples of aprotic polar solvents such as foxide
Can be. This organic solvent has a total amount of monomers of 100 weight
It is preferred to use 20 to 1,000 parts by weight per part.
And more preferably 50 to 500 parts by weight. As the chain transfer agent, mercaptans,
Sulfides and halomethanes are used. The amount of the chain transfer agent depends on the desired copolymerization.
Can be appropriately selected depending on the degree of polymerization of the
0.5 to 500 parts by weight based on 100 parts by weight of the total amount of the monomers.
It is preferably in parts by weight. A more preferred amount is
Depends on the type of chain transfer agent, for example, mercaptan
And 0.5 to 40 parts by weight of disulfide
1 to 80 parts by weight for halomethanes.
The total amount is 2 to 200 parts by weight. Low amount of chain transfer agent
If it is too long, the change over time in the hydrolysis rate will increase,
If the amount is too large, the molecular weight of the resulting oligomer
, And sufficient film-forming properties cannot be obtained. Benzoyl peroxy is used as a polymerization initiator.
Sid, p-chlorobenzoyl peroxide, 2,4-di
Chlorobenzoyl peroxide, tert-butyl peroxide
Toart, methyl ethyl ketone peroxide, cumenech
Organic peroxides such as dropperoxide and azobisui
Sobutyronitrile and the like can be exemplified. The amount of the polymerization initiator used is 1
The amount is preferably 0.01 to 10 parts by weight based on 00 parts by weight.
The higher the amount of the polymerization initiator used, the easier it is to obtain a low polymer.
In particular, when a chain transfer agent is not used in combination, the monomer 1
It is preferable to use 1 to 10 parts by weight with respect to 00 parts by weight.
New The polymerization temperature is preferably from 50 to 200 ° C.
More preferably, it is 60 to 130 ° C. The polymerization temperature is
The higher the temperature within the range, the better the purpose of the present invention.
The obtained copolymer is easy to obtain. When no chain transfer agent is used
Preferably, the polymerization is carried out at 90 to 200 ° C. The production method of the present invention
(A) in the prepared triorganosilyl group-containing copolymerbird
Organosilyl group-containing unitTriorgano in some side chains of
Silyl groups having two or more silicon functional groups
Ester with a functional compound or its partial hydrolyzate
By performing the exchange reaction, (C)Silyl group-containing silicon
Functional unitTo obtain a silicon-functional copolymer containing
Sign. In addition, the above ester in the presence of a trace amount of water
Multiple silicon functional groups can be simultaneously
To form a crosslinked structure, or once
(C) unit is formed by the method of
After the condensation, a condensation reaction is
Thus, a condensation crosslinked product can be obtained. In the transesterification reaction of the present invention, siliconization
As described above, the compound represented by the general formula (R⁸)_aSix
_4-a(Where R⁸, X and a are as described above)
Is used.R ⁸ As
Is methyl, ethyl, propyl, butyl, pentyl,
Examples of alkyl groups such as xyl; and vinyl groups
And a methyl group or a vinyl group is preferred. X
As, in addition to the above hydroxyl group, methoxy, ethoxy,
Alkoxy groups such as propoxy and butoxy; 2-methoxy
Alkoxya such as ethoxy, 2-ethoxyethoxy, etc.
Alkoxy group; alkenyloxy such as isopropenoxy
Group; acyloxy group such as acetoxy; acetoneoxy
And ketoxime groups such as methylethylketoxime;
Tylamino, butylamino, hexylamino, cyclohexyl
Organoamino groups such as xylamino; diethylamino
Diorganaminoaminooxy group such as xy; N-methylaceto
Examples include organoamide groups such as amides.
Methoxy, ethoxy and acetoxy groups are preferred.
New Silicon-functional compoundsAs methyl silicate
, Ethyl silicate, propyl silicate, methyl
Limethoxysilane, vinyltrimethoxysilane, methyl
Triethoxysilane, vinyltriethoxysilane, methyl
Rutripropoxysilane, methyl tris (methoxy eth
Xysilane), methyl tris (ethoxyethoxysila)
), Methyltriisopropenoxysilane, methyltri
Acetoxysilane, vinyltriacetoxysilane, methyl
Rutri (acetone oxime) silane, methyl tri (methyl
Ruethylketoxime) silane, methyltri (N-methyl)
Acetamido) silane, phenyltrimethoxysilane,
Dimethyldimethoxysilane, dimethyldiethoxysilane
Examples of such silane compounds and their hydrolysates
it can. Of these, it is easily available and transesterified
Because the reaction and crosslinking reaction can be easily and well controlled,
Methyltrimethoxysilane, methyltriethoxysila
, Methyltriacetoxysilane and the corresponding
Vinylsilane is preferred. For the triorganosilyl group-containing copolymer
The amount of the silicon-functional compound forms the unit (C) described below.
That's enough to do. The transesterification can be carried out at room temperature.
However, it is more preferable to carry out at 50 to 150 ° C. Ma
Organic solvents to control the reaction and prevent gel formation during the reaction
It is preferable to use This organic solvent includes
The same as that used for the production of the organosilyl group-containing copolymer
The same can be used. The transesterification is carried out in the presence of a catalyst.
This allows the reaction to proceed more quickly
At the same time, a crosslinking reaction can be performed. This catalyst
As dimethylhydroxylamine, diethyl hydride
Roxylamine, tetramethylguanidine, hexylurea
Min, dodecylamine phosphate, γ-aminopropyl tri
Ethoxysilane, N- (trimethoxysilylpropyl)
Amines such as ethylenediamine; benzyltrimethyl
Quaternary ammonium salts such as ammonium acetate;
Iron octoate, iron naphthenate, cobalt octoate, na
Cobalt phenate, manganese octoate, naphthenate
Organic acids such as gangan, tin octoate and tin naphthenate
Metal salt; dibutyltin diacetate, dibriltingio
Octoate, dibutyltin dilaurate, dimethyltin
Monooleate, dibutyltin dimethoxide, diboxide
Organotin compounds such as tiltin; tetrabutyl titane
Metal alcohol such as tetrabutyl zirconate
G; diisopropoxybis (acetylacetonato) tita
Diisopropoxybis (ethylacetoacetate)
Tan, 1,3-propanedioxybis (acetylacetate
Nato) titanium, 1,3-propanedioxybis (ethyl)
Examples of titanium chelates such as acetoacetate) titanium
Can be shown. By such transesterification,
(A) A part of the unit is represented by the general formula (III).
Converted to i-functional silyl (meth) acrylate units
And silicon units comprising (A), (B) and (C) units
A functional copolymer is obtained. In the above general formula (III), R⁷ , R⁸ ,
The definitions of X and a are as described above. Where R⁸ When
Are methyl, ethyl, propyl, butyl, pliers
Alkyl and hexyl; and vinyl
It is possible to easily carry out a crosslinking reaction with X.
For this purpose, a methyl group or a vinyl group is preferred. Also, X
Is to crosslink the copolymer to increase the coating strength of the coating material.
It contributes to improvement. As X
In addition to the above hydroxyl groups, methoxy, ethoxy, propoxy,
Alkoxy groups such as butoxy; 2-methoxyethoxy,
Alkoxyalkoxy groups such as 2-ethoxyethoxy;
Alkenyloxy groups such as isopropenoxy; acetoxy
Acyloxy groups such as thiocyanate; acetone oxime, methylethyl
Ketoxime groups such as uketoxime; diethylamino,
Tylamino, hexylamino, cyclohexylamino
Which organoamino group; Geo such as diethylaminoxy
Lugaminoaminoxy groups; e.g. N-methylacetamide
Examples thereof include a luganamide group.
However, in order to facilitate the crosslinking reaction, a methoxy group
Toxic and acetoxy groups are preferred. A represents the ease of synthesis and the crosslinking reaction of the copolymer.
Since it can be controlled well, it is preferable that the value be 1.
Good. The average degree of polymerization of the silicon-functional copolymer,
That is, the copolymers (A), (B) and (C)
The average value of the sum of the number of places is not particularly limited
However, when the purpose is a gradually soluble coating material, 10-1
00 is preferred. This average degree of polymerization is too small
If it is too small, sufficient film-forming properties cannot be obtained.
No. If it is too large,
Hydrolysis rate is very slow at the beginning of use and satisfactory slow solubility
Rapid hydrolysis rate after a certain period of time
Change in hydrolysis rate over time, such as an increase in
Due to the difficulty, its use as a coating material is limited.
You. The content of the unit (A) in the copolymer
Is preferably in the range of 10 to 90 mol%. This includes
When the content is less than 10 mol%, it is enough for the coating material
Over 90 mol%
In some cases, the mechanical strength of the coating film is not sufficient. In addition
In order to obtain a more preferable slowly soluble coating material,
(A) The content of the unit is in the range of 20 to 50 mol%.
Is preferred. The content of the unit (B) in the copolymer
Is preferably in the range of 10 to 90 mol%,
Preferably it is in the range of 30 to 80 mol%. 10 mol%
If less, sufficient mechanical strength and adhesion
If it exceeds 90 mol%, sufficient slow solubility is obtained.
I can't get it. The content of the unit (C) in the copolymer
Is preferably in the range of 0.01 to 35 mol%,
More preferably, it is in the range of 0.1 to 20 mol%. 0.
If the amount is less than 01 mol%, a frame formed by condensation
Bridge density is reduced, and coating by crosslinking, which is a feature of the present invention, is performed.
Insufficient improvement in the mechanical properties of the film, exceeding 35 mol%
If available, gel during copolymer production or storage.
The stability as a coating material
No. [0037] According to the present invention, a silicon-functional copolymer obtained by the present invention is provided.
The polymer is easily condensed and cross-linked due to its silicon functionality.
Can be formed. These copolymers are controlled
Having a slow hydrolysis rate, and
Bottom paint and fishing nets that prevent aquatic animals from adhering
Forming a coating film showing the required slow solubility of the treatment agent on the surface of the object
Can be In addition, this coating is resistant to temperature changes.
Excellent in mechanical properties. [0038] EXAMPLES The present invention will be described below with reference examples and examples.
I will tell. In the following, all parts are parts by weight. Reference Example 1 A reaction vessel equipped with a cooler, stirrer, and thermometer
300 parts of silene, dimethylhexylsilyl methacrylate
120 parts, methyl methacrylate 180 parts and 1-
6 parts of octanethiol were charged. Then, further azo
After adding 2 parts of bisisobutyronitrile,
While stirring at 80 ° C for 8 hours to polymerize
Performed, light yellow transparent with viscosity of 420 cP at 25 ° C
A dimethylhexylsilyl group-containing copolymer solution was obtained.
This is designated as copolymer solution P-1. The number average molecular weight of this polymer was 4,300.
(By gel permeation chromatography)
Measurement, hereinafter the same). Reference Examples 2 to 5 Solvents, monomers, chains shown in Table 1 in the same manner as in Reference Example 1.
A transfer agent and a polymerization initiator were charged, and the polymerization conditions shown in Table 1 were used.
The polymerization is carried out in each case.
To obtain a polymer solution containing a hydroxyl group (P-2 to P-5, respectively)
Do). The solution viscosity of this copolymer solution at 25 ° C.
The average polymerization degree was as shown in Table 1. [0042] [Table 1]Embodiment 1 Polymerization in reaction vessel equipped with cooler, stirrer and thermometer
100 parts of body solution P-1 is charged, and methyltrimethoxy is added.
After adding 5.0 parts of silane, stir so as to be uniform.
While at 80 ° C. for 10 hours, transesterification
Was done. As a result, the viscosity increases and the viscosity at 25 ° C.
Silicon functionality in the form of a pale yellow transparent solution with a degree of 1,050 cSt
A solution of a condensation crosslinked product of the copolymer was obtained. Examples 2 to 7 Using various polymer solutions, the silane compounds shown in Table 2
Depending on the reaction conditions, transesterification and crosslinking are performed,
All examples are condensation of a pale yellow transparent silicon-functional copolymer
A solution of the crosslinked product was obtained. Dissolution of these solutions at 25 ° C
Table 2 shows the liquid viscosity. [0045] [Table 2]

Claims (1)

(57) [Claims] 1. (A) General formula (I): Embedded image (Where R¹Represents a hydrogen atom or a methyl group;²Is
Same or different from each other,Aliphatic unsaturated bondNot include
Monovalent hydrocarbon groups, at least one of which is
Represents a monovalent hydrocarbon group having 4 or more carbon atoms)G
Liorganosilyl group-containing unit;and (B) General formula (II): Embedded image (Where R³Represents a hydrogen atom or a methyl group, and Z represents,
CO ₂ R ⁴ Group, cyano group, chlorine atom, acetoxy group, O
R ⁵ Group or R ⁶ Selected from the group consisting of ⁴ , R ⁵
Is a substituted or unsubstituted alkyl having 1 to 8 carbon atoms
And R is ⁶ Is a monovalent cyclic group containing a nitrogen atom in the ring
is thereWhich represents a monovalent polar group or a phenyl group)
Repeat unitConsisting of triorganosilyl group-containing copolymer
To The general formula (R⁸)_aSix_4-a (Where R⁸Are the same or different monovalent hydrocarbons
X represents a hydroxyl group,OrAlkoxy group, alco
Xyalkoxy, acyloxy, ketoxime, ol
Ganoamino group, diorganaminoaminoxy group and organo
Selected from the group consisting of amide groupsRepresents a hydrolysable group,
a represents a number from 0 to 2)
And reacting the triorganoside of some side chains of the unit (A).
By transesterifying the ril group, the unit (A)
(B) units, and (C) General formula (III): Embedded image (Where R⁷Is R¹Represents the same group as⁸, X and a
Is shown above)Silyl group-containing silicon functionality
unitCharacterized by obtaining a silicon-functional copolymer consisting of
For producing a silicon-functional copolymer. 2. When the silicon-functional copolymer has (A) units of 10 to 90
%, (B) 10 to 90 mol% and (C) unit
2. The method according to claim 1, comprising 0.01 to 35 mol%.
Law.