CN100509887C - Butylbenzene emulsion, preparing method and application thereof - Google Patents
Butylbenzene emulsion, preparing method and application thereof Download PDFInfo
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- CN100509887C CN100509887C CNB2007100429676A CN200710042967A CN100509887C CN 100509887 C CN100509887 C CN 100509887C CN B2007100429676 A CNB2007100429676 A CN B2007100429676A CN 200710042967 A CN200710042967 A CN 200710042967A CN 100509887 C CN100509887 C CN 100509887C
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Abstract
The present invention discloses one kind of styrene-butadiene emulsion and its preparation process and application. The preparation process includes the following steps: the free radical emulsion polymerization of water solution of mixture of carboxylic acid monomer, butadiene monomer, styrene monomer, molecular weight regulator, emulsifier and initiator for 3-10 hr; regulating the pH value of the resultant to pH 7-10 and filtering. The styrene-butadiene emulsion has high performance and may be used in building paint and papermaking paint to form coating with high water resistance and high adhesion to the base material.
Description
Technical field
The present invention relates to a kind of binding agent, be specifically related to a kind of styrene-butadiene emulsion and preparation method thereof.
Background technology
Styrene-butadiene emulsion is widely used in the bonding of paper coating, building coating, and is in application process, more and more higher to the performance requriements of emulsion.Along with the improvement and the development of emulsion applications Technology, require emulsion to have good technology suitability, wherein, the water tolerance of emulsion film forming, sticking power are important performances.
At present, commercial styrene-butadiene emulsion all beyond reactive tensio-active agent as emulsifying agent, comprise anion surfactant and nonionogenic tenside.
Medium-sized emulsifying agent is behind emulsion film forming, and is compatible with polymer body because of being difficult to, and moves to the surperficial of film easily or the interface that links to each other with base material and make the water tolerance variation of film, and and base material between the sticking power variation.Account for amount of monomer 0.3wt%～1.5wt% as negatively charged ion among the Chinese patent CN1075818C and nonionic compound emulsifying agent add-on, adopt the styrene-butadiene latex of this method preparation to have high stability, but the water tolerance of its emulsion film forming, sticking power is not enough to some extent.
Summary of the invention
The objective of the invention is to propose a kind of styrene-butadiene latex and its production and application, to overcome the defective of prior art.
The preparation method of styrene-butadiene latex of the present invention may further comprise the steps:
The aqueous solution with the mixture of carboxylic acid monomer, divinylic monomer, (methyl) styrene monomer, molecular weight regulator, emulsifying agent and initiator, carry out the free radical emulsion copolymerization under 40 ℃～90 ℃, 0.6MPa～1.0MPa condition, 3～10 hours reaction times, reaction product is regulated pH=7～10 with alkaline matter, the emulsion weight solid content that obtains after filtration is 40%～60%, and median size is 100nm～300nm.
Said carboxylic acid monomer is selected from least a in vinylformic acid, methacrylic acid, toxilic acid, fumaric acid or the methylene-succinic acid;
Said emulsifying agent is a reactive emulsifier, is selected from least a in allyl polyethenoxy ether ammonium sulfate, allyl polyethenoxy ether or the vinyl Soxylat A 25-7.
Said molecular weight regulator is at least a in positive Dodecyl Mercaptan or the tert-dodecyl mercaptan.
Said initiator is selected from least a in Potassium Persulphate, Sodium Persulfate, the ammonium persulphate.
Said alkaline matter is selected from alkali-metal oxyhydroxide, preferred sodium hydroxide, and preferably adopting weight content is 10%～40% aqueous sodium hydroxide solution;
In the technique scheme, in weight (dry weight) per-cent:
The carboxylic acid monomer 0.5%～5%
Divinylic monomer 10%～90%
(methyl) styrene monomer 5%～80%
Molecular weight regulator 0.1%～1%
Emulsifying agent 0.2%～2%
Initiator 0.1%～2%
Adding up to weight is 100%.
Styrene-butadiene emulsion of the present invention can be used for building coating, papermaking paint prescription.
As everyone knows, medium-sized emulsifying agent is behind emulsion film forming, and is compatible with polymer body because of being difficult to, and moves to the surperficial of film easily or the interface that links to each other with base material and make the water tolerance variation of film, and and base material between the sticking power variation.And the present invention adopts reactive surfactant as emulsifying agent, this emulsifying agent can be with the formal bond of chemical bond with on polymer chain, therefore can not migrate to film the surface or with interface that base material links to each other on and water tolerance that can reinforcing membrane, the sticking power between raising and the base material.
Styrene-butadiene emulsion of the present invention is a kind of product that can satisfy building coating, papermaking paint high-performance, environmental protection.This product uses in building coating, papermaking paint, can obviously improve the water tolerance of paint coatings, and the sticking power between the base material.
Embodiment
Embodiment 1
Adding 1 gram weight concentration is 50% allyl polyethenoxy ether ammonium sulfate (the Rhodapex CL910 of Rhodia) aqueous solution in 1000ml compressive reaction still, 5 gram Potassium Persulphates, and 344.5 gram distilled water are dissolved into the aqueous solution fully.Add vinylformic acid 12.5 grams again, divinyl 25 grams, vinylbenzene 197 grams, positive Dodecyl Mercaptan 2.5 grams.
Carry out stirring heating under the 0.6MPa condition, 40 ℃ of Heating temperatures, are carried out polyreaction at 10 hours time.Be cooled to 25 ℃, with the neutralization of 37.5 grams, 20% aqueous sodium hydroxide solution.Filter through 100 eye mesh screens, get high adhesive force, enhanced water resistance styrene-butadiene emulsion, solid content 40.2%, median size 100nm (using Malven particle diameter instrument to record), pH=9.8 (using PHS-3C Accurate pH instrumentation to get).
Embodiment 2
In 1000ml compressive reaction still, add 6 gram 50% allyl polyethenoxy ether ammonium sulfate (the Emulsogen APG2019 of the Switzerland Clariant company) aqueous solution and 6 gram 50% vinyl Soxylat A 25-7 (the Emulsogen R208 of the Switzerland Clariant company) aqueous solution, 0.3 gram Sodium Persulfate, 193.1 gram distilled water is dissolved into the aqueous solution fully.Add methacrylic acid 1.5 grams again, divinyl 51.3 grams, vinyl toluene 240 grams, tert-dodecyl mercaptan 0.3 gram.Carry out stirring heating under the 1.0MPa condition, 90 ℃ of Heating temperatures, are carried out polyreaction at 3 hours time.Be cooled to 25 ℃, with the neutralization of 1.5 grams, 40% aqueous sodium hydroxide solution.Filter through 100 eye mesh screens, get high adhesive force, enhanced water resistance styrene-butadiene emulsion, solid content 59.7%, median size 300nm (using Malven particle diameter instrument to record), pH=7.1 (using PHS-3C Accurate pH instrumentation to get).
Embodiment 3
In 1000ml compressive reaction still, add 6 gram 50% allyl polyethenoxy ether (RhodasurfAAE-10 of Rhodia) aqueous solution, 3 gram ammonium persulphates, 290 gram distilled water are dissolved into the aqueous solution fully.Add methylene-succinic acid 4.5 grams again, divinyl 270 grams, vinylbenzene 15 grams, n-butyl mercaptan 1.5 grams.Carry out stirring heating under the 0.8MPa condition, 70 ℃ of Heating temperatures, are carried out polyreaction at 6 hours time.Be cooled to 25 ℃, with the neutralization of 10 grams, 30% aqueous sodium hydroxide solution.Filter through 100 eye mesh screens, get high adhesive force, enhanced water resistance styrene-butadiene emulsion, solid content 49.6%, median size 195nm (using Malven particle diameter instrument to record), pH=8.1 (using PHS-3C Accurate pH instrumentation to get).
Embodiment 4
In 1000ml compressive reaction still, add 2 gram 50% allyl polyethenoxy ether (RhodasurfAAE-10 of Rhodia) aqueous solution and 1.6 gram 50% allyl polyethenoxy ether ammonium sulfate (the Rhodapex CL910 of Rhodia) aqueous solution, 4.5 gram Potassium Persulphate, 189.65 gram distilled water is dissolved into the aqueous solution fully.Add toxilic acid 10.5 grams again, divinyl 154.8 grams, vinylbenzene 120 grams, positive Dodecyl Mercaptan 2.4 grams.Carry out stirring heating under the 0.9MPa condition, 55 ℃ of Heating temperatures, are carried out polyreaction at 8 hours time.Be cooled to 25 ℃, with the neutralization of 60 grams, 10% aqueous sodium hydroxide solution.Filter through 100 eye mesh screens, get high adhesive force, enhanced water resistance styrene-butadiene emulsion, solid content 54.8%, median size 238nm (using Malven particle diameter instrument to record), pH=8.5 (using PHS-3C Accurate pH instrumentation to get).
Embodiment 5
The method of pressing GB/T 1733-93/ first method detects water-resistance property of coating
The concrete test plate (panel) situation that part is soaked into by deionized water in deionized water of observing.
| Sample | 24 hours | 48 hours | 72 hours |
| Press the sample of the method preparation of CN1075818C | Become blue | Bleach | Bleach |
| Embodiment 1 | No change | The slight indigo plant that becomes | The slight indigo plant that becomes |
| Embodiment 2 | No change | The slight indigo plant that becomes | The slight indigo plant that becomes |
| Embodiment 3 | No change | The slight indigo plant that becomes | The slight indigo plant that becomes |
| Embodiment 4 | No change | The slight indigo plant that becomes | The slight indigo plant that becomes |
Embodiment 6
With embodiment 1～4 with press the styrene-butadiene emulsion of the method preparation of CN1075818C, by following formulation emulsion paint:
| The component title | Specifications and models | Mass parts |
| Water | Deionization | 200.0 |
| Sanitas | TroysanPMA-30 | 1.0 |
| Tetrasodium pyrophosphate | 1.4 | |
| Yelkin TTS | Water dispersible | 4.8 |
| Defoamer | Nopco1719-B | 4.0 |
| Rutile TiO 2 | 225.0 | |
| Kaolin | Hydrite?flat?D | 125.0 |
| Magnesium Silicate q-agent | Nytal?300 | 125.0 |
| Thickening material | Keltex?P?2％ | 25.0 |
| The mill base subtotal | 711.2 |
Said components is added high speed dispersor, the back high speed dispersion 20～30min that stirs, qualified to fineness, low speed adds following component down, and after stirring, discharging is filtered;
| Styrene-butadiene emulsion | 309.4 | |
| Thickening material | Keltex?P?2％ | 154.5 |
| Mill base | 711.2 | |
| Add up to | 1175.1 |
Adopt the emulsion paint of above-mentioned formulation, press GB 9266-88 method and detect the coating abrasion resistance
| Sample | Abrasion resistance |
| Press the sample of the method preparation of CN1075818C | Scrub 1506 wearing and tearing obviously |
| Embodiment 1 | Scrub 2300 times and do not have wearing and tearing |
| Embodiment 2 | Scrub 2150 times and do not have wearing and tearing |
| Embodiment 3 | Scrub 2203 times and do not have wearing and tearing |
| Embodiment 4 | Scrub 2452 times and do not have wearing and tearing |
From above-mentioned application result as can be seen: use the styrene-butadiene emulsion of the embodiment of the invention 1～4 preparation, compare, can strengthen the sticking power between coating and the base material significantly with comparative example.
Claims (7)
1. the preparation method of a styrene-butadiene emulsion, it is characterized in that, may further comprise the steps: the aqueous solution of the mixture of carboxylic acid monomer, divinylic monomer, (methyl) styrene monomer, molecular weight regulator, emulsifying agent and initiator is carried out the free radical emulsion copolymerization, 3～10 hours reaction times, reaction product is regulated pH=7～10 with alkaline matter, obtain emulsion after filtration; Temperature of reaction is that 40 ℃～90 ℃, reaction pressure are 0.6MPa～1.0MPa;
Said emulsifying agent is selected from least a in allyl polyethenoxy ether ammonium sulfate, allyl polyethenoxy ether or the vinyl Soxylat A 25-7;
Said molecular weight regulator is at least a in positive Dodecyl Mercaptan or the tert-dodecyl mercaptan;
Said initiator is selected from least a in Potassium Persulphate, Sodium Persulfate, the ammonium persulphate.
2. method according to claim 1 is characterized in that, with the dry weight weight percent meter:
The carboxylic acid monomer 0.5%～5%
Divinylic monomer 10%～90%
(methyl) styrene monomer 5%～80%
Molecular weight regulator 0.1%～1%
Emulsifying agent 0.2%～2%
Initiator 0.1%～2%
Adding up to weight is 100%.
3. method according to claim 1 is characterized in that, said carboxylic acid monomer is selected from least a in vinylformic acid, methacrylic acid, toxilic acid, fumaric acid or the methylene-succinic acid.
4. method according to claim 1 is characterized in that said alkaline matter is selected from alkali-metal oxyhydroxide.
5. adopt the styrene-butadiene emulsion of each described method preparation of claim 1～4.
6. styrene-butadiene emulsion according to claim 5 is characterized in that, emulsion weight solid content is 40%～60%, and median size is 100nm～300nm.
7. according to the application of claim 5 or 6 described styrene-butadiene emulsion, it is characterized in that, be used for building coating, papermaking paint prescription.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100429676A CN100509887C (en) | 2007-06-28 | 2007-06-28 | Butylbenzene emulsion, preparing method and application thereof |
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|---|---|---|---|
| CNB2007100429676A CN100509887C (en) | 2007-06-28 | 2007-06-28 | Butylbenzene emulsion, preparing method and application thereof |
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| CN101077902A CN101077902A (en) | 2007-11-28 |
| CN100509887C true CN100509887C (en) | 2009-07-08 |
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| CN101838491B (en) * | 2010-05-21 | 2012-12-05 | 吴承斌 | Preparation method of water-soluble polishing varnish liquid |
| CN103374090B (en) * | 2012-04-13 | 2016-08-24 | 泉州德立化工有限公司 | A kind of soap-free polymerization prepares the method for artificial turf back painting carboxylic styrene butadiene latex |
| CN103539898B (en) * | 2012-07-12 | 2016-05-11 | 中国石油天然气股份有限公司 | Preparation method of easy-to-emulsify powder rubber for modified asphalt |
| CN103113525B (en) * | 2013-01-23 | 2014-10-22 | 宁波佛来斯通新材料有限公司 | Preparation method of low-odor polymer emulsion |
| CN103233399B (en) * | 2013-04-11 | 2016-08-17 | 广东华凯科技股份有限公司 | A kind of latex fiber plate water conservation inorganic agent and preparation method thereof and water-retaining method |
| CN104448150B (en) * | 2013-09-18 | 2017-01-11 | 中国石油天然气股份有限公司 | Preparation method of flame-retardant powdered styrene butadiene rubber |
| CN103524675A (en) * | 2013-09-28 | 2014-01-22 | 昆山市周市溴化锂溶液厂 | Preparation method of modified butylbenzene latex |
| CN105713124A (en) * | 2014-12-04 | 2016-06-29 | 上海东升新材料有限公司 | Butylbenzene emulsion and preparation method and application thereof |
| CN105505017A (en) * | 2015-11-26 | 2016-04-20 | 王学素 | Exterior wall osmol waterproof material |
| CN106967194A (en) * | 2017-04-20 | 2017-07-21 | 上海东升新材料有限公司 | A kind of wallpaper styrene-acrylic latex |
| CN109293813A (en) * | 2017-07-25 | 2019-02-01 | 济宁明升新材料有限公司 | A kind of building coating styrene-acrylic latex and preparation method |
| CN109295805A (en) * | 2017-07-25 | 2019-02-01 | 济宁明升新材料有限公司 | A kind of styrene-butadiene emulsion and its application |
| CN109293833A (en) * | 2017-07-25 | 2019-02-01 | 济宁明升新材料有限公司 | The preparation method of styrene-butadiene latex and products thereof for building coating |
| CN109293832A (en) * | 2017-07-25 | 2019-02-01 | 济宁明升新材料有限公司 | The preparation method of styrene-butadiene emulsion and products thereof for building coating |
| CN109957074A (en) * | 2017-12-14 | 2019-07-02 | 东升新材料（山东）有限公司 | A kind of preparation method and applications of wallpaper carboxylic styrene butadiene latex |
| CN109957068A (en) * | 2017-12-14 | 2019-07-02 | 东升新材料（山东）有限公司 | A kind of U.S. line paper carboxylic styrene butadiene latex and its preparation method and application |
| CN109957069A (en) * | 2017-12-14 | 2019-07-02 | 东升新材料（山东）有限公司 | A kind of preparation method and applications of U.S. line paper carboxylic styrene butadiene latex |
| CN110409216A (en) * | 2018-04-27 | 2019-11-05 | 东升新材料（山东）有限公司 | A kind of wallpaper styrene-butadiene latex and its preparation method and application |
| CN108914688A (en) * | 2018-08-21 | 2018-11-30 | 济宁明升新材料有限公司 | A kind of styrene-butadiene emulsion and its preparation method and application |
| CN109183498A (en) * | 2018-08-21 | 2019-01-11 | 济宁明升新材料有限公司 | A kind of preparation method and application of wallpaper carboxylic styrene butadiene latex |
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Denomination of invention: Butylbenzene emulsion and its preparing method and application Effective date of registration: 20191225 Granted publication date: 20090708 Pledgee: Bank of Hangzhou, Limited by Share Ltd, Shanghai branch Pledgor: Shanghai Dongsheng New Materials Co., Ltd. Registration number: Y2019310000035 |
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Date of cancellation: 20210813 Granted publication date: 20090708 Pledgee: Bank of Hangzhou Limited by Share Ltd. Shanghai branch Pledgor: SHANDONG DONGSHENG NEW MATERIAL Co.,Ltd. Registration number: Y2019310000035 |