JPH0247115A - Vinyl esters and their use in building industry - Google Patents

Abstract

PURPOSE: To provide vinyl esters which is useful for the repair of a concrete material or a surface hardened at an ambient temperature by blending a vinyl compound shown by a specific formula, a vinyl compound other than the cited, if necessary with a polymerization catalyst.

CONSTITUTION: (A) a compound shown by formula I [R is H, CH₃; R¹ is straight-chained or branched-chained C_2-8 alkylene; n is 1-10; R₂ is a group of formula II, formula III, formula IV or the like and R₃ is straight-chained or branched-chained C_1-22 alkyl, straight-chained or branched-chained C_2-22, (substituted) C_5-6 cycloalkyl (cyclohexyl or cyclopentyl), phenyl, naphthyl or the like], (B) a vinyl compound except formula I, if necessary, and (C) 0.1-10% based on the weight of the component A; B) of more than two kinds of polymerization catalyst are blended to thereby provide vinyl esters. This compound is impregnated into or coated on a porous material, especially concrete, by using independently or together with a bulking agent, then, for example, a crack can be repaired by filling it and hardening it at a surrounding temperature.

COPYRIGHT: (C)1990,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION According to the invention, a) 2I where R is hydrogen or methyl, R1 is a linear or branched C2 alkylene, and n is one of I to 10; is an integer, R is a formula a) to i), where R1 is a linear or branched C+ Cz□ alkyl group, a linear or branched cz C20, non-monosubstituted or substituted C, -C, cycloalkyl (cyclohexyl or cyclopentyl), phenyl, naphthyl, where A is C, -C alkylene or C2-C, alkenylene, and R11 is hydrogen or acetyl and RIS is C
+ Ch alkyl compound (hereinafter component a)
b) If necessary, one or more vinyl compounds other than the formula (hereinafter referred to as components), and c) O, 1 to 10%. (based on the weight of components a and b) (hereinafter referred to as component C), all percentages are based on the weight of the composition.

Preferably from 20 to 10 based on the total weight of monomers.
0, more preferably 50-95% of components a and 0-8
0, more preferably 5 to 50% of the component is present in the composition according to the invention.

The composition according to the invention preferably contains: d) 40 to 95% of inorganic aggregate (hereinafter referred to as component d) based on the total weight of the composition.

Polymerization catalysts (component c), such as organic hydroperoxides and aromatic amine promoters and optionally polyvalent metal salts or complex salts, can be added to the monomer mixture before application. The proportion of metal salts or complex salts added to the composition before application is from 0.0005% to about 2% by weight, and the amount of hydroperoxide is from 0.1 to 5% by weight, based on the total weight of monomers. %. Similarly,
The functional peroxide can be added to the mixture before application, together with an aromatic amine promoter and optionally a polyvalent metal salt or complex salt. The proportion of organic peroxide to the composition can range from 0.5 to 5% by weight, and the aromatic amine promoter is present in an effective amount,
It is usually used in a range of about 0.1 to 5% by weight.

The components of the polymerization catalyst, such as the polyvalent metal salt or complex salt and the hydroperoxide, and the amine promoter or aromatic amine promoter and peroxide, are packaged separately and transported to the work site, where the respective components are combined. , and therein the compositions of the invention can be applied by impregnation or sealing into concrete floors or foundations or pavements, for example by pouring or spraying.

Alternatively, the aromatic amine accelerator and binder monomer systems, and the organic peroxide (optionally together with the salve), respectively, may be stored and transported together in a package, so that they can be used together. After forming the composition of the invention, the composition is applied.

The polyvalent metal salt or complex salt used in the present invention is any polyvalent metal-containing salt that catalyzes the oxidative curing of drying oils and, when added to oil-based varnishes and paints, accelerates their drying or curing. be able to. These metal salts or complex salts are also known in the art as [siccative or dryer]. Such materials include polyvalent metal salts of higher aliphatic or nanthenic acids having from 8 to 30 carbon atoms that provide solubility in the binder monomer system. Generally, the dryer salts most useful in the compositions of this invention are Nanthenic or C,-C,. They are salts of aliphatic acids. Examples of polyvalent metals include calcium, copper, zinc, manganese, manganese, lead, cobalt, iron, vanadine, and zirconium.

These salts or complex salts accelerate the action of organic hydroperoxides and promote oxidative curing in organic peroxide-amine catalyst systems.

Other examples of dryer salt onic acid components or anions include resin acids, 2-ethylhexanoic acid, lauric acid, palmitic acid, myristic acid, stearic acid, oleic acid, linoleic acid, behenic acid, cerotic acid, monotanoic acid
anic acid) and those of abietic acid.

Preferably the dryer salts are those of cobalt and manganese, such as cobalt octoate, cobalt naphthenate, cobalt acetylacetonate and manganese octoate, manganese naphthenate, and manganese acetylacetonate.

Aromatic amines are used in small amounts with organic peroxides and generally accelerate the action of the peroxides. For example, aniline, N, N-dimethylaniline, N,
N-diethylaniline, toluidine, N,N-dimethyl p-toluidine, N,N di(hydroxyethyl)toluidine, and p-dimethylaminobenzaldehyde with 0.0% of the binder monomer system. It can be added in an amount of 1-2% by weight.

Organic peroxides and hydroperoxides that can be used include those derived from hydrocarbons having about 3 to 18 carbon atoms so as to be soluble in the binder monomer system.

Suitable organic hydroperoxides include tert-butyl hydroperoxide, cumene hydroperoxide, methyl ethyl ketone hydroperoxide and diisopropylbenzene hydroperoxide. Suitable peroxides include benzoyl peroxide, tert-butyl perbenzoate, dilauryl peroxide, di(4-tert-butyl-cyclohexyl)-peroxide dicarbonate, 2,2-bis(tert-butylperoxy)-butane, bis- Includes (1-hydroxy-cyclohexyl)-butane, bis-(1-hydroxy-cyclohexyl)-peroxide, and tert-butylperoxy-isopropyl carbonate.

Preferred polymerization catalysts are mixtures of organic peroxides and aromatic aminos. A more preferred polymerization catalyst is a mixture of benzoyl peroxide or cumene peroxide and N,N-dimethyl p-)luidine.

Particularly preferred polymerization catalysts are mixtures of p-dimethylaminobenzaldehyde, benzoyl peroxide or cumene peroxide and cobalt naphthenate.

The aggregate (component d) used here as necessary is:
Organic and inorganic acids, salts and alkalis that may be encountered in common industrial plants, such as hydrochloric acid, sulfuric acid, nitric acid, sulfonic acid, phosphoric acid, acetic acid, formic acid; salts of sodium, potassium, calcium and manganese, such as It can be an inert inorganic material resistant to chlorides, sulfates and alkali metal and alkaline earth metal hydroxides. Examples of suitable aggregates include sand, silica powder, quartz, granite, feldspar, gneiss, basalt, porphyry rocks or crushed stones and small stones thereof.

The sand that can be used can be of any quality or size. Graded sands of medium particle size, such as "ottawa J sand and "best" sand or mixtures thereof, can be used more advantageously. Ottawa sand is "round"
d) It is a type of silica sand called J. The best sand is the type known as "sharp". In both cases, fines will be removed. However, in general, the size of the sand sieve can vary over a fairly wide range.

Instead of or in addition to sand, crushed colored glass marbles, crushed glass, silica powder, emery powder,
Slag grinding and fine gravel can be used.

Furthermore, according to the invention, three package compositions are adapted for use together: a first package consisting of components a and b, a second package consisting of component C and a third package consisting of component d; is provided.

The second and third packages can be combined, or the first and third packages can be combined.

Preferably R1 is R1', where R is -CH
2-C11□-; 2H5-co, -cLi-CH2-CH-or-(CIH
2) 6-CH.

It is.

Preferably n is 1.

Preferably R2 is R2r, where R2 has the formula a'
or b' where R3' is as defined below.

Preferably, in the composition according to the invention, the compound of formula (1) is CH,=C-Co-0R11-0-R2'
(II) is a compound of the formula wherein the symbols are as defined above.

Preferably the components are of the formula i) where R is as defined above and R4 is a straight or branched C,-C22 alkyl (said alkyl is unsubstituted or or substituted with one or more (preferably 1 to 3) groups selected from hydroxy, carboxy, thio or amido groups), or R4 is cycloalkyl,
phenyl, naphthyl, wherein A and RI5 are as defined above in Section 1 above, 11) compounds of the formula ■ substituted), and ■) compounds of the formula ■ where R, R, and n are as defined above in paragraph 1 above, Rza is a, "-e+ where R, R, and n are as defined above, RIO is a radical of the formula in which R12 is hydrogen, an alkali metal or alkaline earth metal cation, or a mono-, di- or tri-C, -C, alkylamine, where the amine is unsubstituted or A group consisting of three ○H groups, in which Rz is hydrogen or acetyl.

Preferably, component C is 0.1 to 5% by weight of 03C111
Hydrocarbyl peroxide or 03C1ll hydrocarbyl hydroperoxide and o,oos~2% by weight of polyvalent metal salt or complex salt and/or 0.1~5%
of aromatic amino group-containing polymer promoters, all percentages are based on the weight of components a and b.

Furthermore, according to the present invention, the formula (1) CH2=C-co.-(oRl). Compounds are provided: a-o-R2(V), where na is an integer from 2 to 10, and the other symbols are as defined above.

Further according to the present invention there is provided a compound of formula XX wherein the symbols are as defined above.

Furthermore, according to the present invention, in the formula 2XIV a , R1 is methyl and R3 is C9°-CIl! A compound of car' other than alkyl, and the other symbols are as defined above, is provided.

Compounds of 2I in which R2 is of formula a) to e) are prepared by: i) 1 mol of one anhydride of formula LL with 1 mol of a compound of formula XVI R3-OH(XI,'I); , reacted at high temperature to form the formula X■0H-
Produce a compound of RZ (X■),
Then 1i) 1 mol of a compound of formula X■ is added to 1 mol of a compound of formula XIXH
O-(R,-0). -)1 (XIX) at high temperature to react with a compound of formula XXlR20(R
IO)-H(XH) in which R2 is as defined above, and then convert 1 mole of the compound of formula XXI to 1 mole of formula XχllC
It can be produced by reacting with a compound of H2,,C-C0OH(XXII) at high temperature to produce a compound of formula (1).

In the above reaction, elevated temperature means a temperature of 40-110°C.

Compounds of formula (1), in which R3 is not alkenyl, have a) 1 mole of formula (2) CH2=C-Co-0-(R1-0)rl, -OH(v
II) is reacted with 1 mole of the above acid anhydride of formula L-LV at elevated temperature to form formula ■ R, 11-0-(R,O), -Co-C=CH.

/(veeee) where the symbols are as defined above, the compound of formula ■ is optionally salified by reaction with an alkali, and then b) 1 mole of formula ■ A compound or a salt thereof is prepared at an elevated temperature to form 1 mol of a compound of formula IX Rz At (IX) in which:
A1 can be prepared by reacting with the compound, which is a group that can be cleaved from R3.

Other compounds of formula (1) can be prepared from known compounds by known methods.

Preferred compounds of formula IX (7) are R, -0-5o-CI
,C.

C, alkyl or cycloalkyl-chlorosulfide, di-R3-sulfate, tri-R.

phosphate, tri-R3-phosphite or R3-
halogen (in a suitable solvent such as hexamethylphosphoric triamide). The reaction can also be carried out in the presence of isonitrile and CuzO.

Preferably, the elevated temperature for reaction a) is 80-110"C and for reaction b) 40-60"C.

The compound of 2XX can be prepared by a similar method by formula
a is 1) and a compound of formula 2 (R2° is a group of formula a1).

Compounds of formula It can be prepared by

Compound 2, when n is 1 and R2m is derived from acrylic acid, is known or can be prepared from known compounds by known methods.

A methyl ester of a compound of formula (e.g. when R3 is methyl) is reacted with a linear or branched aliphatic alcohol by known methods (e.g. in the presence of an alkali catalyst), Suitable aliphatic alcohol esters can be produced.

Compounds of formula (1) can be prepared from appropriate reactants by known methods.

Compounds 2) can be prepared by methods analogous to those for forming compounds of formula I from the appropriate reactants.

The compound of 2V is the compound of the formula xn CH2=C-C0OH (XI Engineering). In the middle, the symbol is as defined above, and the compound at high temperature (
For example, it can be prepared by reacting at 40 to 60°C.

Further according to the invention, at least 3 repeating units of formula XX
X-[C)l, -C-Co-(OR,). -O
R2] (XXX) in the formula,
A homopolymer or copolymer containing, where the symbols are as defined above, optionally together with 40 to 90% (based on the weight of the total composition) of component d is provided.

Preferably, the number of repeating units of formula XXX is from 3 to 50.

The compositions according to the invention containing components a [optionally components], c and d are useful for the repair of concrete materials or surfaces. Such compositions are applied to the surface in need of repair and allowed to cure at ambient temperature.

the composition or compound according to the invention is alone;
For example, crevices can be filled.

Once on flame, 1 mole of fucuric anhydride is reacted with 1 mole of methacrylic acid glycol ester at a temperature of about 100°C to produce an intermediate of formula 1□.

Formula 1. neutralize the compound with sodium hydroxide, and
React with 0.5 mol of dimethyl sulfate at 0°C.

The compounds of formula 1 defined below are liquids and the viscosities are measured on a Brookfield viscometer, spindle 2 at 60 rpm and are reported in the table below. In a similar way, we further obtain Eq.
Compounds of the formula (wherein the symbols are as defined in the table) can be obtained from the appropriate reaction components.

Compound of Example 1 and Formula 1. Mix the intermediate with aggregate and catalyst according to the following recipe.

sand 229
．． 2g Silica Huyum 23.2g
Compound of Formula 1 of Example 1 42.75 g Formula 1
1 combination! p7I 2.25g dimethylaminobenzaldehyde 1.8g cumene hydroperoxide 0.9g cobalt naphthenate 00g The composition cures within 15 minutes and after 12 hours.
Can be tested for strength. Packing aggregates, monomers and catalysts into different packages for shipment to the construction site.

Claims (1)

[Claims] 1, a) Formula I ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (I) In the formula, R is hydrogen or methyl, and R_1 is a linear or branched C_2-C_8 is alkylene, n is an integer from 1 to 10, R_2 is a formula a) to i), ▲There are mathematical formulas, chemical formulas, tables, etc.▼(a) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(b ) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (c) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (d) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (e) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (f) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (g) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (h) or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (i) In the formula, R_3 is a straight chain or branched C_1-C_2_2
Alkyl group, linear or branched C_2-C_2
_2, unsubstituted or substituted C_5-C_6 cycloalkyl (cyclohexyl or cyclopentyl), phenyl, naphthyl, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ , where A is C_1-C_6 alkylene or C_2-C_6 alkenylene, R_1_1 is hydrogen or acetyl, and R_1
_5 is C_1-C_6 alkyl, one or more compounds (hereinafter referred to as component a), and b) optionally a vinyl compound other than formula I (hereinafter referred to as component a);
one or more of component b); and c) 0.1 to 10% (based on the weight of components a and b).
(hereinafter referred to as component c), all percentages are based on the weight of the composition. 2. The composition according to item 1 above, containing 20 to 100% of component a and 80% of component b. 3. The above first composition containing 40 to 95% inorganic aggregate based on the total weight of the composition.
Or the composition according to item 2. 4.Compound a has formula II ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) In the formula, R_1' is -CH_2-CH_2-; ▲mathematical formula, chemical formula,
There are tables, etc.▼；▲There are mathematical formulas, chemical formulas, tables, etc.▼
or -(CH_2)_6-, and R_2' is the formula a' or b' ▲There are mathematical formulas, chemical formulas, tables, etc.▼(a') Yes, in the formula, R_3' is a linear or branched C_1_-_1_
2 alkyl or C_2_-_1_2 alkenyl group, and R is hydrogen or methyl, the composition according to any one of items 1 to 3 above. 5. Component b is i) Formula III ▲ Numerical formula, chemical formula, table, etc. ▼ (III) where R is as defined above, and R_4 is a linear or branched C_1- C_2_2
is alkyl (said alkyl is unsubstituted or substituted by one or more (preferably 1 to 3) groups selected from hydroxy, carboxy, thio or amido groups); or R_4 is cycloalkyl, phenyl, naphthyl; A compound of formula IV ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (IV) In the formula, R, R_1 and n are as defined above in the above paragraph 1, and R_2_a is a_1-e_1 ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (a_1) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (b_1) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (c_1) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ( d_1) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (e_1) is the group, where R_1_3 is hydrogen, an alkali metal or alkaline earth metal cation, or a mono-, di- or tri-C_1-
C_8 alkylamine (the amine is unsubstituted or substituted with 1 to 3 OH groups)
, and iii) a compound of formula V ▲Mathematical formula, chemical formula, table, etc.▼(V) where R, R_1 and n are as defined above, and R_1
＿0 is the group of the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼▲There are mathematical formulas, chemical formulas, tables, etc.▼ ▲There are mathematical formulas, chemical formulas, tables, etc.▼▲There are mathematical formulas, chemical formulas, tables, etc.▼ The composition according to any one of the above items 1 to 4, wherein R_1_1 is hydrogen or acetyl. 6. Component c is 0.1-5% by weight of C_3-C_1_8 hydrocarbyl peroxide or C_3-C_1_8 hydrocarbyl hydroperoxide and 0.005-2
% by weight of polyvalent metal salts or complex salts and/or from 0.1 to
6. A composition according to any of the preceding clauses, wherein the composition is a promoter combination of 5% of an aromatic amino group-containing polymer, all percentages being based on the weight of components a and b. 7.Formula VI ▲Mathematical formulas, chemical formulas, tables, etc.▼(VI) In the formula, R is hydrogen or methyl, R_1 is linear or branched C_2-C_8 alkylene, and na is 2 to R_2 is an integer of 10, and R_2 is a formula a) to i) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (a) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (b) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (c) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (d) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (e) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (f) ▲ Mathematical formulas, chemical formulas, tables, etc. Yes ▼ (g) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (h) or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (i) In the formula, R_3 is linear or branched C_1-C_2_2
Alkyl group, linear or branched C_2-C_2
_2, unsubstituted or substituted C_5-C_6 cycloalkyl (cyclohexyl or cyclopentyl), phenyl, naphthyl, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, and in the formula, A is C_1-C_6 alkylene or C_2-C_6 alkenylene, R_1_1 is hydrogen or acetyl, and R_1
A compound in which _5 is C_1-C_6 alkyl. 8.Formula XX ▲Mathematical formulas, chemical formulas, tables, etc.▼(XX) In the formula, R is hydrogen or methyl, and R_3 is a linear or branched chain C_1-C_2_2
Alkyl group or linear or branched C_2-C
_2_2 alkenyl, unsubstituted or substituted C_5-C
_6 cycloalkyl (cyclohexyl or cyclopentyl), phenyl, naphthyl, ▲Mathematical formulas, chemical formulas, tables, etc. are available▼ or ▲Mathematical formulas, chemical formulas, tables, etc. are available▼, where A is C_1-C_6 alkylene or C_2-C_6 alkenylene, R_1_1 is hydrogen or acetyl, and R_1
A compound in which _5 is C_1-C_6 alkyl. 9.Formula
Alkyl group or linear or branched C_2-C
_2_2 alkenyl, unsubstituted or substituted C_5-C
_6 cycloalkyl (cyclohexyl or cyclopentyl), phenyl, naphthyl, ▲Mathematical formulas, chemical formulas, tables, etc. are available▼ or ▲Mathematical formulas, chemical formulas, tables, etc. are available▼, where A is C_1-C_6 alkylene or C_2-C_6 alkenylene, R_1_1 is hydrogen or acetyl, and R_1
A compound in which _5 is C_1-C_6 alkyl, provided that R_3 is other than C_1_0-C_1_8 alkyl. 10, the formula described in item 1 above, where R_2 is formula a) to e)
A method for preparing a compound of I, i) 1 molar formula L-LIV ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (L) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (L I) ▲ Mathematical formulas, chemical formulas , tables, etc. ▼ (LII) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (LIII) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (LIV
) is reacted with 1 mole of a compound of formula XVI R_3-OH (XVI) at elevated temperature to form a compound of formula XVIIOH
-R_2(XVII) and then ii) 1 mole of the compound of formula XVII is added to 1 mole of the compound of formula XIXH
O-(R_1-O)_n-H(XIX) is reacted with a compound of formula XX I R at high temperature.
_2-O-(R_1-O)_n-H(XX I),
R_2 is as defined above, and then iii) converting 1 mole of the compound of formula XX I to 1 mole of the compound of formula XX
A process characterized in that the compound of formula I is produced by reacting with a compound of IICH_2=C-COOH(XXII) at an elevated temperature.