CN1049672C - Method for cross-linking polymer emulsion using unsatured epoxy resin at room temp - Google Patents
Method for cross-linking polymer emulsion using unsatured epoxy resin at room temp Download PDFInfo
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- CN1049672C CN1049672C CN91107026A CN91107026A CN1049672C CN 1049672 C CN1049672 C CN 1049672C CN 91107026 A CN91107026 A CN 91107026A CN 91107026 A CN91107026 A CN 91107026A CN 1049672 C CN1049672 C CN 1049672C
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Abstract
The present invention relates to a crosslinking method of polymer emulsion at a room temperature with unsaturated epoxy resin. Unsaturated carboxylic acid (anhydride) and a small amount of tertiary amine are added into epoxy resin to react at the temperature of 70 to 130DEG C to prepare the unsaturated epoxy resin; the unsaturated epoxy resin is used as an activated monomer copolymerized with 95 to 60% (measured by the total monomer weight) of emulsion of other vinyl unsaturated monomers in the presence of an anionic/nonionic mixed surface active agent to obtain the polymer emulsion with a side chain containing an epoxy group; 60 to 200% (measured by the epoxy equivalent value) of organic polyamine is added into the copolymerized emulsion to obtain the polymer emulsion crosslinked at the room temperature. The present invention has the advantages of simple and convenient technology, low price of the raw materials and easy obtainment of the raw materials. The crosslinking degree of the polymer after being crosslinked at the room temperature can reach 70 to 100%.
Description
The present invention relates to a kind of method that adopts the unsatured epoxy resin at room temp cross-linking polymer emulsion.
Prior art is the method that adopts with the epoxy resin at room temp cross-linking carbonyl bearing polymer emulsion.This method is to introduce Resins, epoxy in polymer emulsion or its preparation process, and it requires to contain in the system a certain amount of free carboxyl group.Because the existence of free carboxyl group, when adding organic amine curing agent, the viscosity of emulsion can produce growth by a relatively large margin.On the other hand, because at room temperature speed of response is slower for carboxyl and epoxy group(ing), so cross-linked network of the final cross-linked polymer that forms, it will be cross-linked network based on the ionic linkage structure, polymkeric substance with this cross-linked network structure, it is water-fast and alkali resistance will be poor than the cross-linked polymer that is made of the chemical bond cross-linked network structure.
Purpose of the present invention provides a kind of normal temperature crosslinked method that overcomes above-mentioned insufficient polymer emulsion---with the method for unsatured epoxy resin at room temp cross-linking polymer emulsion.It can make the realization of most polymers emulsion normal temperature crosslinked with raw material cheap and easy to get and easy operating procedure.
Technical solution of the present invention: the unsaturated carboxylic acid (acid anhydride) (in equivalents) with Resins, epoxy and 25～50% was prepared undersaturated Resins, epoxy in 0.5～10 hour 70～130 ℃ of reactions under 0.2～1% tertiary amine (in weight epoxy) catalysis; With the gained unsatured epoxy resin is reactive monomer, and in the presence of the anionic/nonionic mixed surfactant, the unsaturated vinyl monomer emulsion copolymerization with 95～60% makes the polymer emulsion that side chain contains epoxy group(ing); Contain in the polymer emulsion of epoxy group(ing) at side chain then, add organic polyamine in Ahew number 60～200% (to the epoxide equivalent number).
The Resins, epoxy that uses among the present invention is for containing the Resins, epoxy of two epoxy group(ing), as E-55, E-51, E-44, E-42 and E-20 etc.Use lower molecular weight, the Resins, epoxy of high epoxy value has better effect.
The unsaturated carboxylic acid that uses among the present invention is monobasic or the di-carboxylic acid (acid anhydride) that contains a unsaturated double-bond.As (methyl) vinylformic acid, maleic acid (acid anhydride), methylene-succinic acid etc.The ratio of unsaturated carboxylic acid and Resins, epoxy by equivalence ratio should be 1: 2.0～1: 4.0.But the tertiary amine of catalysis carboxylic acid and Resins, epoxy reaction has: triethylamine, N.N-dimethyl benzylamine, and 2,4,6-(N.N-dimethylaminomethyl)-phenol etc., its consumption is 0.2～1% of a weight epoxy.
When using unsatured epoxy resin and other monomer copolymerization to prepare room temperature cure polymer emulsion among the present invention, the unsatured epoxy resin consumption should account for 5～40% of total monomer, and emulsion copolymerization can adopt the emulsion polymerisation process of knowing to carry out.As a feeding method, monomer dropping semi-continuous emulsion polymerizing method, monomer emulsion drips semi-continuous emulsion polymerizing method and seeded emulsion polymerization method.Can have with the vinyl monomer of unsatured epoxy resin copolymerization: (methyl) acrylics monomer, vinyl acetate between to for plastic, propylene are fine, (methyl) vinylformic acid, acrylamide, N hydroxymethyl acrylamide, (methyl) acrylic acid hydroxy alkyl ester, vinylbenzene, vinylchlorid, vinylidene chloride, ethene, propylene, divinyl etc.Emulsion copolymerization should be adopted negatively charged ion and nonionic blended tensio-active agent, wherein anionic surface live the ratio of agent and tween should be 1: 3～2: 1.Spendable anion surfactant has sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, polyxyethylated alkylphenol sodium sulfate, polyxyethylated alkylphenol sodium phosphate and Succinic Acid modification polyxyethylated alkylphenol (OS, auxiliary reagent factory, Shanghai produce) etc., nonionogenic tenside has: polyxyethylated alkylphenol series, polyoxyethylene polyoxypropylene block copolymer and peregal series etc.The emulsifying agent consumption is generally 1～7% of monomer weight.
Contain in the polymer emulsion of epoxy group(ing) at the above-mentioned side chain that makes, add organic amine curing agent, promptly get normal temperature crosslinked polymer emulsion.Spendable organic amine solidifying agent is aliphatic amide, modified fatty amine or other amine that contains two or more primary amine or secondary amine, as diethylenetriamine, triethylene tetramine, tetraethylene pentamine, T31 solidifying agent (auxiliary reagent factory, Kunshan, Jiangsu product), Versamid etc., the consumption of organic amine curing agent, in the Ahew number, be 60～200% of epoxy equivalent (weight) number.
Use method of the present invention, available raw material cheap and easy to get and easy technology realize normal temperature crosslinked to the most polymers emulsion.Polymer emulsion crosslinking degree after normal temperature crosslinked can reach 70～100%.
Embodiment 1
(1) preparation of unsatured epoxy resin:
In 500 milliliters of there-necked flasks that whipping appts, reflux condensing tube, thermometer and oil bath heating are housed, add 250 gram E-51 Resins, epoxy (oxirane value 0.52), 31 gram vinylformic acid, 0.03 gram Resorcinol and 0.63 gram N.N---dimethyl benzylamine, 95 ℃ of following stirring reactions 5 hours, get acid number 0.69, the unsatured epoxy resin of oxirane value 0.31.
(2) preparation of normal temperature crosslinked polymer emulsion:
Component: A. water 110 grams
OP 4.5 grams
(polyoxyethylene phenolic ether in the ninth of the ten Heavenly Stems, the auxiliary reagent factory, Shanghai produces)
OS 3.75 grams
(Succinic Acid modification OP, 40% water
Solution, the auxiliary reagent factory, Shanghai produces)
Sodium lauryl sulphate 1,5 gram B. vinylformic acid formicesters 150 grams
Ethyl acrylate 80 grams
N-dodecyl mercaptan 0.2 gram
Unsatured epoxy resin 60 gram C. vinylformic acid 5.0 grams by (one) preparation
Ammoniacal liquor (26%) 3.4 gram D. n-methylolacrylamide 5 grams
Water 10 gram E. water 297 grams
OP 4.5 grams
OS 3.75 grams
Sodium lauryl sulphate 1.5 grams
Sodium phosphate dibasic 1.6 grams
Ammonium persulphate 0.3 gram F. ammonium persulphate 1.0 grams
Water 10 grams
In the 500mL there-necked flask of whipping appts and dropping funnel is housed, add component A, under agitation add B component, C and D successively, add the back and continue to stir 1.5 hours, promptly get stable monomer emulsion.
Water bath with thermostatic control is being housed, whipping appts, thermometer, reflux condensing tube, in 1 liter of four-hole boiling flask of nitrogen ingress pipe and dropping funnel, feed nitrogen earlier, fully oxygen is wherein fallen in displacement, then with warming-in-water to 70 ℃, 10% (i.e. 43.3 grams) that under agitation add component E and above-mentioned monomer emulsion, continue under this temperature, to keep 20 minutes after observing blue look fluorescence, then with interior temperature rise to 75 ℃ monomer emulsion and the F component of being left that add even in 3 hours, after adding with interior temperature rise to 85 ℃, and under this temperature, kept 1 hour, cooling discharging promptly gets and contains 40% admittedly, the emulsion of viscosity 0.075Pa.s.
Get 100 parts of above-mentioned emulsion, adding Resins, epoxy T31 solidifying agent (auxiliary reagent factory, Kunshan, Jiangsu produces, Ahew 55～70) 2.0 grams, blending emulsion is 91.8% through film forming and in room temperature (25 ℃, down together) crosslinked one all backs degree of crosslinking.
Embodiment 2
(1), the preparation of unsatured epoxy resin:
The preparation method is with embodiment 1 it (), but prescription is:
E-44 Resins, epoxy 250 grams
(oxirane value 0.45)
Methacrylic acid 48.4 grams
Resorcinol 0.075 gram
2,4,6-(N.N-dimethylaminomethyl)-phenol 1 gram
Through 110 ℃ of reactions 1 hour, get acid number 18, the unsatured epoxy resin of oxirane value 0.22.
(2), the preparation of normal temperature crosslinked polymer emulsion:
With embodiment 1 they (two), but B component, D change into:
B, vinylformic acid formicester 173 grams
Ethyl acrylate 100 grams
Lauryl mercaptan 0.2 gram
Unsatured epoxy resin 15 grams by (one) preparation
D, n-methylolacrylamide 7 grams
Water 14 restrain solids content 39.7%, the emulsion of viscosity 0.13Pa.s.Get this emulsion 100 grams, add T31 solidifying agent 0.55 gram, blending emulsion is through film forming and after a normal temperature crosslinked week, and degree of crosslinking is 74%.
Embodiment 3
(1) preparation of unsatured epoxy resin:
The preparation method is with embodiment 1 it (), but prescription changes into:
E-42 Resins, epoxy 250 grams
(oxirane value 0.40)
Toxilic acid 14.5 grams
Resorcinol 0.02 gram
Triethylamine 1.5 grams
Through 130 ℃ of reactions 40 minutes, get acid number 2.6, the unsatured epoxy resin of oxirane value 0.29.
(2) preparation of normal temperature crosslinked polymer emulsion:
Identical with embodiment 1 they (two), but wherein B component, E change into:
B. vinylformic acid formicester 60 restrains
Ethyl acrylate 40 grams
Butyl acrylate 70 grams
Unsatured epoxy resin 120 grams by (one) preparation
E. water 293 restrains
OP 7.5 grams
OS 3.75 grams
Sodium lauryl sulphate 1.5 grams
Sodium phosphate dibasic 1.6 grams
Ammonium persulphate 0.3 restrain contain 40% admittedly, the emulsion of viscosity 0.05Pa.s.Above-mentioned emulsion 100 gram adds tetraethylene pentamine 1.3 grams, mixed emulsion through or film and normal temperature crosslinked one all after degree of crosslinking 93%.
Embodiment 4
(1) unsatured epoxy resin preparation:
Press embodiment 1 it () with the quadrat method preparation, but prescription is:
E-51 Resins, epoxy 250 grams
Vinylformic acid 33.4 grams
Resorcinol 0.05 gram
N.N-dimethyl benzylamine 2.5 grams
Through 70 ℃ of reactions 10 hours, get acid number 5.5, the unsatured epoxy resin of oxirane value 0.31.
(2) normal temperature crosslinked polymer emulsion preparation:
Identical with embodiment 1 they (two), but wherein B component, E change into:
B vinyl acetate between to for plastic 73.5 grams
Vinylformic acid formicester 36.7 grams
Methymethacrylate 12.3 grams
Butyl acrylate 122.5 grams
(1) unsatured epoxy resin 45 grams of preparation
E. water 191 restrains
OP 4.5 grams
OS 3.75 grams
Sodium lauryl sulphate 1.5 grams
Sodium phosphate dibasic 1.6 grams
Ammonium persulphate 0.45 restrain the emulsion of solids content 47.2%, viscosity 0.84Pa.s.In above-mentioned emulsion 100 gram, add T31 solidifying agent 2.1 grams, the gained blending emulsion through film forming and after a normal temperature crosslinked week degree of crosslinking be 86%.
Embodiment 5
(1) unsatured epoxy resin preparation
The preparation method is with embodiment 1 it (), but formula adjustment is:
E-44 Resins, epoxy 250 grams
Maleic anhydride 15.8 grams
Resorcinol 0.02 gram
N.N-dimethyl benzylamine 0.7 gram gets acid number 2.0 through 100 ℃ of reactions 4.5 hours, the unsatured epoxy resin of oxirane value 0.30 gram.
(2) preparation of normal temperature crosslinked polymer emulsion
With embodiment 1 they (two), but component B changes into:
B. vinylformic acid formicester 150 gram Ethyl acrylates 80 gram n-dodecyl mercaptans 0.2 gram (one) prepared unsatured epoxy resin 60 restrain solid content 40.1%, the emulsion of viscosity 0.08Pa.s.In above-mentioned emulsion 100 gram, add 0.7 triethylene tetramine, the gained blending emulsion through film forming and after the normal temperature crosslinked week degree of crosslinking be 90%.
Embodiment 6
With embodiment 1, but the T31 solidifying agent is reduced to 0.86 gram by 1.87 grams.Gained emulsion normal temperature crosslinked one all backs degree of crosslinking is 77%.
Embodiment 7
With embodiment 1, but T31 solidifying agent 1.87 gram changes 300 type Versamids, 3.8 grams into, the gained blending emulsion through film forming and after normal temperature crosslinked ten days degree of crosslinking be 82%.
The measuring method of degree of crosslinking: with polymer emulsion film forming on the tetrafluoroethylene plate, seasoning at room temperature or vacuum-drying, after the room temperature certain hour is crosslinked, take by weighing 0.5～1.5 gram solid polymerization matter sample in apparatus,Soxhlet's, carry 5 hours continuously with acetone, the remaining weight of polymkeric substance and the ratio of primary sample weight are the degree of crosslinking of polymkeric substance.The measurement of each sample repeats 3 times.
Claims (4)
1, a kind ofly prepare the method for room temperature cross-linking polymer emulsion, it is characterized by with Resins, epoxy:
(1) Resins, epoxy and 25～50% unsaturated carboxylic acid (acid anhydride) (in equivalents) were prepared undersaturated Resins, epoxy in 0.5～10 hour 70～130 ℃ of reactions under 0.2～1% tertiary amine (in weight epoxy) catalysis;
(2) be reactive monomer with the gained unsatured epoxy resin, in the presence of the anionic/nonionic mixed surfactant, the unsaturated vinyl monomer emulsion copolymerization with 95～60% makes the polymer emulsion that side chain contains epoxy group(ing);
(3) contain in the polymer emulsion of epoxy group(ing) at side chain, add organic polyamine in Ahew number 60～200% (to the epoxide equivalent number).
2, the method with the unsatured epoxy resin at room temp cross-linking polymer emulsion according to claim 1 is characterized in that said Resins, epoxy is the Resins, epoxy that contains two epoxide groups;
3, the method with the unsatured epoxy resin at room temp cross-linking polymer emulsion according to claim 1 is characterized in that said unsaturated carboxylic acid (acid anhydride) is for containing the monocarboxylic acid or the di-carboxylic acid (acid anhydride) of a α, β unsaturated double-bond.
4, the method with the unsatured epoxy resin at room temp cross-linking polymer emulsion according to claim 1 is characterized in that said organic polyamine is the organic amine that contains at least two primary amine or secondary amine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN91107026A CN1049672C (en) | 1991-05-06 | 1991-05-06 | Method for cross-linking polymer emulsion using unsatured epoxy resin at room temp |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN91107026A CN1049672C (en) | 1991-05-06 | 1991-05-06 | Method for cross-linking polymer emulsion using unsatured epoxy resin at room temp |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1055746A CN1055746A (en) | 1991-10-30 |
| CN1049672C true CN1049672C (en) | 2000-02-23 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN91107026A Expired - Fee Related CN1049672C (en) | 1991-05-06 | 1991-05-06 | Method for cross-linking polymer emulsion using unsatured epoxy resin at room temp |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1049672C (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102796261A (en) * | 2012-07-31 | 2012-11-28 | 广州星业科技股份有限公司 | Polyamine derivative, as well as preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63371A (en) * | 1986-06-19 | 1988-01-05 | Mitsui Toatsu Chem Inc | Underwater curing corrosion-resistant material composition |
| EP0400226A1 (en) * | 1988-01-06 | 1990-12-05 | Nippon Shokubai Co., Ltd. | Resin composition |
-
1991
- 1991-05-06 CN CN91107026A patent/CN1049672C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63371A (en) * | 1986-06-19 | 1988-01-05 | Mitsui Toatsu Chem Inc | Underwater curing corrosion-resistant material composition |
| EP0400226A1 (en) * | 1988-01-06 | 1990-12-05 | Nippon Shokubai Co., Ltd. | Resin composition |
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| Publication number | Publication date |
|---|---|
| CN1055746A (en) | 1991-10-30 |
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