CN1025623C

CN1025623C - Preparation method of synergistic acrylic acid thickening agent

Info

Publication number: CN1025623C
Application number: CN 91111575
Authority: CN
Inventors: 罗弘; 吕书仁; 邓翠萍
Original assignee: EAST CHEMICAL PLANT BEIJING
Current assignee: Beijing Chemical Industry Refco Group Ltd; Dongfang Chemical Plant
Priority date: 1991-12-13
Filing date: 1991-12-13
Publication date: 1994-08-10
Anticipated expiration: 2006-12-13
Also published as: CN1060664A

Abstract

The invention relates to a preparation method of a synergistic acrylic thickener, which comprises methacrylic acid, itaconic acid, lower alkyl acrylate, higher alkyl acrylate, acrylamide and a reactive surface active type. The method adopts a batch feeding emulsion polymerization method, the solid content of the product is 15-30%, the pH value is 3-5, the self viscosity is less than 20Mpa.s, and the product can be used as an aqueous system thickener and can be used in emulsion paint, tile adhesive, relief paint, pressure-sensitive adhesive, fabric coating, carpet back adhesive, detergent, cosmetics and oil well drilling.

Description

Jointing acrylic acid thickening agent and made method

The invention relates to a kind of preparation method who increases the thickening material of water medium viscosity, more particularly about the preparation method of synergism type acrylic thickeners.

The report of relevant thickening material is a lot of in the prior art, at United States Patent (USP) 4,432, a kind of thickening material is disclosed in 881, this thickening material comprises a kind of the have water-soluble polymers of hydrophobic side group and the tensio-active agent that a kind of used water is disperseed, the hydrophobic grouping that it has hydrophobic grouping and energy and polymkeric substance combines, its composition comprises a kind of water-soluble monomer and comonomer such as dodecylacrylate or methacrylic ester with hydrophobic grouping such as acrylamide, when such multipolymer combined with the tensio-active agent that contains hydrophobic grouping, water viscosity increased when the result formed thickening material and adds entry.

And a kind of water-dispersible hydrophobic thickener, wherein compositions such as acrylamide, vinylformic acid, methacrylic acid, vinylformic acid higher alkyl esters and water miscible metal inorganic salt are further disclosed in U.S. Patent application 79/107,819.When being sheared, when heating or high density ionogen, the water medium of thickening can keep being applicable to the viscous liquid of the viscosity of needs, is applicable to do in the oil well probing etc.

Need be pointed out that in the prior art, do not have as yet up to now with similar techniques of the present invention to be disclosed and to report.

One of purpose of the present invention provides a kind of preparation method that can increase the thickening material of water medium viscosity.

Two of purpose of the present invention provides a kind of emulsion paint that is suitable for, colo(u)rant dispersion, fabric coating, the preparation method of the thickening aqueous systems agent of purposes such as oil well probing.

These purposes of the present invention and all the other purposes will further embody by following specific descriptions and illustrate.

Water dispersible thickening material in order to thickening aqueous systems of the present invention comprises:

1, a kind of vinyl unsaturated carboxylic acid 30-67mt%

2, a kind of α, β vinyl unsaturated carboxylic acid alkyl ester

30-50mt%

3, a kind of α, β vinyl unsaturated carboxylic acid higher alkyl esters

2-20mt%

4, a kind of vinyl unsaturated amides 1-10mt%

5, a kind of response type surfactant active 0.5-10mt%

Among the present invention, if not refer in particular to, all compositions are than all being weight percentage.

In the present invention, the vinyl unsaturated carboxylic acid can be selected from methacrylic acid, vinylformic acid, methylene-succinic acid, toxilic acid, methylene-succinic acid, can select above-mentioned a kind of use, also can select above-mentioned two kinds or multiple using with.

α, β-vinyl unsaturated carboxylic acid alkyl ester can be selected from alkyl acrylate, is preferably to have following structural formula:

R ₁Alkyl for 2-4 carbon.

α, β-vinyl unsaturated carboxylic acid higher alkyl esters can be selected from the senior alkane ester of alkyl acrylic, is preferably to have following structural formula:

R wherein ₂Be H or CH ₃, R ₃Be the alkyl of 8-20 carbon, can from vinylformic acid dodecane ester, methacrylic acid dodecane ester, vinylformic acid tridecane ester, tridecyl methacrylate(TD-, vinylformic acid tetradecane ester, methacrylic acid tetradecane ester, vinylformic acid 16, octadecane ester, methacrylic acid 16, octadecane ester etc., select best.

The vinyl unsaturated amides can be selected from acrylamide and derivative, is preferably to have following structural formula:

Wherein, R ₄Alkyl, alkaryl for H or 8-30 carbon.As acrylamide, fumaramide, 2-acrylamide-2-methyl-prop acid iodide, N-(dimethylaminomethyl) acrylamide, N-(trimethyl ammonium methyl) acrylamide chlorination thing, N-(trimethyl ammonium methyl)-the Methacrylamide muriate etc.

Response type surfactant active preferably has following structural formula in the present invention:

R wherein ₅Be H or CH ₃, R ₆Be the alkyl of 8-20 carbon, alkaryl, n are 5-100.

Come preparation feedback type tensio-active agent by method as described below.

Acrylic or methacrylic acid is pressed 1-20 with alkylphenol polyoxyethylene ethanol: 1, be preferably 5-15: 1 mixed in molar ratio, add a little Resorcinol and oxidation inhibitor, add-on can be 10-10000ppm, be preferably 100-5000ppm, oxidation inhibitor can be common commonly used, and it is commonly used that catalyzer can be selected this professional domain, be preferably the vitriol oil, add-on can be about about 1%.At 90-140 ℃, be preferably 100-130 ℃, reacted 1-5 hour, promptly make the response type surfactant active of effective ingredient more than 50% after being preferably 2-4 hour.

Prepare water dispersible thickening material of the present invention by following disclosed method.

A, a kind of α with 30-50mt%, β-vinyl unsaturated carboxylic acid alkyl ester, wherein alkyl is a 2-4 carbon atom, a kind of α, β-vinyl unsaturated carboxylic acid higher alkyl esters with 2-20mt%, alkyl wherein is a 8-20 carbon atom, and a kind of response type surfactant active of 0.5-10mt% mixes, under agitation join in the mixed aqueous solution of negatively charged ion and nonionic emulsifying agent, and then add the vinyl unsaturated carboxylic acid of 30-67mt% and the vinyl unsaturated amides of 1-10mt%, obtaining monomer concentration is the pre-emulsified monomer mixed solution of 26-74mt%;

B, with persulphate and sulphite with the appropriate amount of deionized water dissolving with the preparation initiator solution, be that this professional domain technician is known in the add-on of this initiator.

C, elder generation add a small amount of rebasing negatively charged ion and nonionic emulsifying agent and part deionized water in reactor, be warming up to 30-60 ℃ and drop into the pre-emulsified monomer mixed solution of part, its ratio is at least 20% of pre-emulsified monomer total amount, distinguish the aqueous solution initiated polymerization of dropping oxidizing agent and reductive agent then, after about 5-30 minute, the system temperature of charge is elevated to 45-70 ℃ voluntarily;

D, when treating that temperature of charge drops to 30-60 ℃, drop into the pre-emulsified monomer mixed solution of another part, its ratio should not be lower than 20%, continue to drip initiator solution, system temperature will rise again, repeat above-mentioned steps for several times, all add, also can select the method for disposable whole inputs up to pre-emulsified monomer mixed solution.

Can be at this negatively charged ion and nonionic emulsifying agent from alkyl and alkaryl sulfuric acid an alkali metal salt, select in alkyl and the alkaryl polyoxyethylene glycol, dodecyl phenenyl sulfate for example, sodium lauryl sulphate, succsinic acid alkyl ester sodium sulfonate, alkane phenolic group polyoxyethylene glycol vitriol is selected in the OP series emulsifying agent etc., as selection preferably, negatively charged ion of the present invention and nonionic emulsifying agent have following structure:

R ₁-(OCH ₂CH ₂) _m-OSO ₆N _aWith

R ₂-（OCH ₂CH ₂） _n-OH

R wherein ₁, R ₂For alkyl, aralkyl, the m of 4-20 carbon is 5-40, n is 10-80, preferably n/2.

In pre-emulsion, the amount ratio of negatively charged ion and nonionic emulsifying agent is 1: 10-10: 1, be preferably 2: 8-8: 2.The rebasing emulsifying agent that adds in initial action is the 5-20% of total amount.

The emulsion polymeric product solid content of preparing with method of the present invention is between 15-30%, pH is 2-5, oneself viscosity is very low, less than 20mpa.s, but the viscosity of the water slurry of its 2% solids concn (regulating the pH value is 7-8) can reach 5,000-50000mpa.s flow index is between-0.8～0.4, molecular weight is 1000-200000.

This product can be used in the prescriptions such as emulsion paint, glue for tile, caulk compound, textured paint, colo(u)rant dispersion, pressure sensitive adhesive, fabric coating, carpet back-adhesive, washing composition, makeup, oil well probing and pharmacy as the thickening aqueous systems agent.

The following examples are only set forth the design of example, and except the elaboration of dependent claims, they can not limit the scope of the invention, and unless otherwise noted, each five equilibrium and per-cent are all based on weight percent.

Example 1

At first take by weighing an amount of vinylformic acid and alkylphenol polyoxyethylene ethanol by 6: 1 mixed in molar ratio, the Resorcinol and the BHT that add 500ppm, make catalyzer with the vitriol oil that accounts for total amount 2%, be reflected between 100-130 ℃ and carry out, after about 2.5 hours, promptly make and contain the response type surfactant active of effective ingredient more than 50%.

Take by weighing the 30Kg butyl acrylate, the response type surfactant active of 15Kg lauryl methacrylate and 0.5Kg mixes, under agitation join in the negatively charged ion and the mixed aqueous solution of nonionic emulsifying agent of 3Kg by preparation in 1: 8, can be Sodium dodecylbenzene sulfonate and alkylphenol polyoxyethylene respectively at this negatively charged ion and nonionic emulsifying agent, the water yield of adding is the 80-90% of total amount.And then add the acrylamide of 49Kg vinylformic acid and 5.5Kg, and stir, make monomer concentration and be 45% pre-emulsified monomer mixed solution.

The sulphite that takes by weighing 1.0Kg persulphate and 0.5Kg with the 2Kg deionized water dissolving to be made into initiator solution.

The rebasing negatively charged ion and nonionic emulsifying agent and the surplus deionized water that in jacket reactor, add total amount 10-20%, be warming up to 40 ℃, drop into the pre-emulsified monomer that accounts for pre-emulsified monomer total amount 30%, drip the aqueous solution of initiator, after about 15 minutes, system temperature is increased to 50 ℃ voluntarily.

Treat that temperature of charge drops to 42 ℃, the pre-emulsified monomer of otal investment 30% drips initiator, system temperature raises, and treats that temperature of charge drops to 40 ℃, drops into the pre-emulsified monomer of residue again, drip initiator, treat that temperature of charge drops to 40 ℃, insulation for some time promptly gets product.

With the emulsion polymeric product that a process for preparing, solid content is 20%, and pH is 4, and oneself viscosity is 15mpa.s, and molecular weight is about 40000, is suitable in the fabric coating.

Example 2

Repeat the step method of example 1, the raw material that only uses is methacrylic acid and the acrylic acid mixture of 30Kg, the ethyl propenoate of 30Kg, the methacrylic acid 16 of 20Kg, stearyl, the acrylamide of 10Kg and the response type surfactant active of 10Kg, the product solid content that makes is 25%, pH is 5, oneself viscosity is 18mpa.s, and molecular weight is about 50000, is suitable for doing in the emulsion paint.

Example 3

Repeat the step method of example 1, the raw material that only uses is 60Kg methylene-succinic acid, vinylformic acid, the mixture of methacrylic acid, the ethyl propenoate of 20Kg, the mixture of butyl ester, the methacrylic acid 16 of 15Kg, stearyl, the acrylamide of 5Kg, the product solid content that makes is 30%, and pH is 4.6, and oneself viscosity is 19mpa.s, molecular weight is about 60000, is suitable for doing glue for tile and uses.

Example 4

Repeat the step method of example 1, the raw material that only uses is the methacrylic acid of 55Kg, the butyl acrylate of 30Kg, the methacrylic acid 16 of 10Kg, stearyl, the acrylamide of 4Kg, the response type surfactant active of 1Kg, the product solid content that makes is 28%, pH is 4.7, oneself viscosity is 14mpa.s, molecular weight is 20,000, and the suitable drilling well conditioning agent of doing is used.

Example 5

At first take by weighing an amount of vinylformic acid and alkylphenol polyoxyethylene ethanol by 15: 1 mixed in molar ratio, add the Resorcinol of 1500ppm and the conventional oxidation inhibitor of other convention amount, as BHT, make catalyzer with 1% the vitriol oil that accounts for total amount, being reflected at 115 ℃ carries out, after about 3 hours, promptly make and contain the response type surfactant active of effective ingredient more than 50%.

Take by weighing the 40Kg butyl acrylate, the response type surfactant active of 18Kg lauryl methacrylate and 0.5Kg mixes, under agitation join in the negatively charged ion and the mixed aqueous solution of nonionic emulsifying agent of 4Kg by preparation in 1: 6, at this negatively charged ion and nonionic emulsifying agent respectively with example 1, the water yield that adds is 90% of a total amount, and then add the acrylamide of 38Kg methylene-succinic acid and 4.5Kg, stirring and making monomer concentration is 70% pre-emulsified monomer mixed solution.

The sulphite that takes by weighing 1.5Kg persulphate and 0.4Kg with the 3Kg deionized water dissolving to be made into initiator solution.

The rebasing negatively charged ion and nonionic emulsifying agent and the surplus deionized water that in jacket reactor, add total amount 10%, be warming up to 50 ℃, drop into the pre-emulsified monomer that accounts for pre-emulsified monomer total amount 20%, drip the aqueous solution of 1/5 initiator, about 30 minutes, system temperature was increased to 45 ℃ voluntarily.

Treat that temperature of charge drops to 45 ℃, drop into the pre-emulsified monomer of remaining amount, drip the residue initiator, system temperature raises, and treats that temperature drops to 40 ℃, is incubated 1 hour and promptly makes product.

With the emulsion polymeric product that a process for preparing, solid content is 18%, and pH is 4.1, and oneself viscosity is 13mpa.s, and molecular weight is 25000, is suitable for washing composition.

This professional domain technician can make many variations and change according to content disclosed by the invention, but all should understand within the scope of the invention, limited by the application's claim scope.

Claims

1, a kind of preparation method of the water dispersible thickening material in order to thickening aqueous systems is characterized in that may further comprise the steps:

A, a kind of α with 30-50mt%, β-vinyl unsaturated carboxylic acid alkyl ester, wherein alkyl is a 2-4 carbon atom; With a kind of α, β-vinyl unsaturated carboxylic acid higher alkyl esters of 2-20mt%, alkyl wherein is a 8-20 carbon atom; And a kind of response type surfactant active of 0.5-10mt% mixes, under agitation join in the mixed aqueous solution of negatively charged ion and nonionic emulsifying agent, and then add the vinyl unsaturated carboxylic acid of 30-67mt% and the vinyl unsaturated amides of 1-10mt%, obtaining monomer concentration is the pre-emulsified monomer mixed solution of 26-74mt%;

B, with persulphate and sulphite with appropriate amount of deionized water dissolving preparation initiator solution;

C, elder generation add a small amount of rebasing negatively charged ion and nonionic emulsifying agent and part deionized water in reactor, be warming up to 30-60 ℃, drop into the pre-emulsified monomer mixed solution of part, ratio is at least 20% of pre-emulsified monomer total amount, distinguish the aqueous solution initiated polymerization of dropping oxidizing agent and reductive agent then, reacted 5-30 minute, the system temperature of charge is elevated to 45-70 ℃ voluntarily;

O, etc. temperature of charge when dropping to 30-60 ℃, drop into the pre-emulsified monomer mixed solution of another part, its ratio should not be lower than 20%, continue to drip initiator solution, system temperature will rise again, repeat above-mentioned steps for several times, all add, also can adopt the method that once all adds up to pre-emulsified monomer mixed solution;

E, treat that temperature of charge drops to 60 ℃, be incubated 1 hour.

2, the preparation method of water dispersible thickening material as claimed in claim 1 is characterized in that described vinyl unsaturated carboxylic acid can select from methacrylic acid, vinylformic acid, methylene-succinic acid.

3, the preparation method of water dispersible thickening material as claimed in claim 1 is characterized in that described α, β-vinyl unsaturated carboxylic acid alkyl ester can be an alkyl acrylate, and following structural formula is arranged:

R ₁Alkyl for 2-4 carbon.

4, the preparation method of water-dispersion thickening material as claimed in claim 1 is characterized in that the senior alkane ester of described α, β-vinyl unsaturated carboxylic acid can select from the senior alkane ester of alkyl acrylic, be preferably to have following structural formula:

R wherein ₂For or CH ₃, R ₃Alkyl for 8-20 carbon.

5, the preparation method of water dispersible thickening material as claimed in claim 1 is characterized in that described vinyl unsaturated amides can select from acrylamide and derivative thereof, be preferably to have following structural formula:

Wherein, R ₄Be the alkyl of H or 8-30 carbon, alkaryl.

6, the preparation method of water dispersible thickening material as claimed in claim 1 is characterized in that described response type surfactant active preferably has

7, the preparation method of water dispersible thickening material as claimed in claim 1 is characterized in that described response type surfactant active prepares as follows:

Acrylic or methacrylic acid is pressed 1-20 with alkylphenol polyoxyethylene ethanol: 1 mixed in molar ratio, add a little Resorcinol and oxidation inhibitor, use sulphuric acid catalysis, promptly make the promoting agent of effective ingredient more than 50% 90-140 ℃ of reaction after 1-5 hour.

8, the preparation method of water dispersible thickening material as claimed in claim 1 is characterized in that prepared composition solid content is 5-30%, and pH is 2-5, and viscosity is less than 20mps.s, and molecular weight is 1000-200000.