CN1513889A - High elasticity acetal phenyl propyl soapless copolymerized emulsion and its preparation - Google Patents
High elasticity acetal phenyl propyl soapless copolymerized emulsion and its preparation Download PDFInfo
- Publication number
- CN1513889A CN1513889A CNA031391087A CN03139108A CN1513889A CN 1513889 A CN1513889 A CN 1513889A CN A031391087 A CNA031391087 A CN A031391087A CN 03139108 A CN03139108 A CN 03139108A CN 1513889 A CN1513889 A CN 1513889A
- Authority
- CN
- China
- Prior art keywords
- soapless
- phenyl propyl
- vinyl acetate
- vinylbenzene
- monomer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
A high-elasticity non-soap copolymer emulsion is prepared from acrylate, vinyl acetate, styrene, acrylonitrile, water-soluble acrylic acid or acrylamide as modifier through copolymerizing in water medium under existance of trigger and pH buffer. Its advantages are high elasticity, long storage time (3 years), high elongation at break (1000%), and self cross-linking and self thickening nature.
Description
Technical field
The present invention relates to a kind of is vinylbenzene, vinyl acetate between to for plastic, acrylic ester ternary polymerization Emulsion Adhesive and the preparation technology thereof of main monomer with the acrylate, belongs to the high molecular polymer technical field.
Background technology
Emulsified acrylic acid is a tackiness agent, compares with solvent-borne type, owing to do not contain organic solvent, therefore has low cost, advantage pollution-free, safe in utilization.
Because acrylic ester monomer can be with comparalive ease and other vinyl monomer copolymerization, so can design different prescriptions as required to satisfy different service requirementss.Vinyl acetate between to for plastic, vinylbenzene, acrylic ester ternary polymerization emulsion are exactly to have gathered the advantage of benzene emulsion, acrylate and vinyl acetate emulsion, pure-acrylic emulsion, thereby can be widely used in the preparation of environmentally-friendly coating materials such as roofing waterproof paint, snappiness exterior coating, building sealant, body of a motor car weld seam seal gum.
The patent No. is " acrylic ester-styrene-vinyl acetate-copolymerized water emulsion " patent of invention of 87100921, is exactly a kind of water-latex type copolymer emulsion, and is the same with traditional emulsion polymerization technique, has two defectives: 1. need to make with extra care before the starting monomer polymerization.Usually need spent ion exchange resin absorption, alkali cleaning or distillatory pretreatment technology, to remove stopper and Vinyl Acetate Monomer hydrolysate acetate and the acetaldehyde in depositing that exists in acrylic ester monomer, the styrene monomer.Pretreatment technology is not only wasted time and energy, and has increased cost; 2. because emulsion polymerization technique is a polymerization technique in the presence of emulsifying agent, cause final copolymer emulsion still to contain emulsifying agent, this makes and has reduced bonding strength and water tolerance behind the emulsion dry solidification.Causing with the emulsion is that the wallcovering goods of tackiness agent are loss of adhesion, scrubbing resistance not, and the seal gum goods reduce intensity, and the coated material waterproof ability is relatively poor.
Summary of the invention
The present invention is promptly at the shortcoming of above-mentioned polymkeric substance and polymerization technique, and a kind of emulsifier-free emulsion polymerization technology, the prescription of preparing the snappiness acetal phenyl propyl soapless copolymerized emulsion and method of adopting proposed, the speed of response that common emulsifier-free emulsion polymerization exists is slow to overcome, the shortcoming of system poor stability, and can omit the refining pretreated loaded down with trivial details technology of monomer.
The present invention realizes with following technical scheme:
In order to realize emulsifier-free emulsion polymerization, the present invention introduces the comonomer of band hydrophilic active group in system, the monomer that contains carboxyl: as vinylformic acid, methacrylic acid, the monomer of hydroxyl, amino: as N hydroxymethyl acrylamide, N, N DMAA, Hydroxyethyl acrylate, Propylene glycol monoacrylate etc.The monomer of these band hydrophilic active groups is as the modification composition, crosslinking reaction can take place when emulsion film forming, can significantly improve cohesive strength and cementability, in addition, the effect that promotes polymerization rate and improve stability is also arranged, its mechanism is: 1. increased the aqueous phase monomer concentration, helped the raising of speed of reaction; 2. the monomer of band hydrophilic active group tends to be arranged on polymer billet-aqueous phase interface when copolymerization, or forms hydration layer with ion or non-ionic form, plays the stabilization of similar emulsifying agent.
Introduce ionizable initiator, as Potassium Persulphate, ammonium persulphate etc., and at the initiator of reaction disposable adding 70% of starting stage and the pH value buffer reagent for preparing with sodium bicarbonate or Sodium phosphate dibasic, make it after decomposition, form the ionic free radical, this just makes that being reflected at the starting stage provides a large amount of free radicals with regard to excessive initiator is arranged, after initiation reaction, the initiator fragment finally is distributed in the emulsion particle surface as the end group of polymkeric substance, can not only play the stabilization that is similar to ionic emulsifying agent, and excessive initiator can be eliminated stopper in the starting monomer to the disadvantageous effect of polyreaction.Owing to set up stable pH value buffer system, not only speed of response is improved, and helps the stable of reactive system.
Raw material and consumption:
1) organic monomer: one or more in methyl acrylate, methyl methacrylate, ethyl propenoate, Hydroxyethyl acrylate, Propylene glycol monoacrylate, butyl acrylate, the 2-EHA, vinylbenzene, vinyl acetate between to for plastic, vinyl cyanide, vinylformic acid and/or methacrylic acid, the N hydroxymethyl acrylamide of acrylic amide and/or N, the N DMAA.Consumption unit is by weight counted:
Vinyl acetate between to for plastic 12-15
Vinylbenzene 12-16
Esters of acrylic acid 59-72
Acrylic amide 1.5-3
Acrylic acid or the like 1-4
Vinyl cyanide 0-8
Above-mentioned monomer consumption is considered as 100 parts;
2) pH value buffer reagent: sodium bicarbonate or Sodium phosphate dibasic.0.2～0.6 part of consumption;
3) initiator: Potassium Persulphate or ammonium persulphate.0.3～1 part of consumption;
4) the deionized water consumption is 80～150 parts.
Polymerization technique:
In reactor, add a certain amount of deionized water, be warming up to 60 ℃, low whipping speed is under the 80-120 rev/min of stirring, good initiator and the buffer reagent of disposable adding 70% dissolving, continue to be heated to 80～85 ℃, respectively the aqueous solution (the dropping time was controlled at 4 hours) of parallel dropping mix monomer and acid amides.Drip after two hours, begin to drip the initiator of residue 30% and buffer reagent and mix monomer, amide aqueous solution and drip simultaneously, be incubated 1 hour after adding.Cool to below 40 ℃, filter discharging.
The prepared vinegar phenylpropyl alcohol ternary of the present invention does not have the soap copolymer emulsion, has very high elasticity and long stability in storage, and its elongation at break can reach 1000%, and the shelf lives is more than 3 years, and have self-crosslinking, from the characteristic of thickening.
Embodiment
Embodiment 1:
Vinylbenzene 16
Vinyl acetate between to for plastic 15
Butyl acrylate 47
Ethyl propenoate 12
Hydroxyethyl acrylate 4.5
Vinylformic acid 4
N hydroxymethyl acrylamide 1.5
Sodium phosphate dibasic 0.2
Potassium Persulphate 1
Water 100
Embodiment 2:
Vinylbenzene 12
Vinyl acetate between to for plastic 15
Butyl acrylate 59
Vinyl cyanide 8
Vinylformic acid 4
N, N DMAA 2
Sodium bicarbonate 0.6
Potassium Persulphate 0.5
Water 80
Embodiment 3:
Vinylbenzene 12
Vinyl acetate between to for plastic 13
Butyl acrylate 60
Methyl methacrylate 7
Propylene glycol monoacrylate 5
Methacrylic acid 1
N hydroxymethyl acrylamide 1.5
Sodium phosphate dibasic 0.3
Ammonium persulphate 0.6
Water 120
Embodiment 4:
Vinylbenzene 15
Vinyl acetate between to for plastic 12
2-EHA 63
Vinyl cyanide 4
Methacrylic acid 3
N, N DMAA 3
Sodium bicarbonate 0.5
Ammonium persulphate 0.3
Water 150
Claims (8)
1. snappiness acetal phenyl propyl soapless copolymerized emulsion, it is characterized in that, emulsion is by one or more of monomer vinyl acetate between to for plastic, vinylbenzene, vinyl cyanide, esters of acrylic acid, described esters of acrylic acid is first, second, fourth, 2--ethylhexyl, hydroxyl ethyl ester, hydroxypropyl acrylate or methyl methacrylate, under pH value buffer reagent and action of evocating, in water medium with water-soluble active monomer acrylic amide one or both, vinylformic acid, methacrylic acid soap-free polymerization forms, described acrylic amide is N hydroxymethyl acrylamide and N, the N DMAA.
2. according to the described snappiness acetal phenyl propyl soapless copolymerized emulsion of claim 1, it is characterized in that its starting monomer consists of:
Vinyl acetate between to for plastic 12-15
Vinylbenzene 12-16
Esters of acrylic acid 59-72
Acrylic amide 1.5-3
Acrylic acid or the like 1-4
Vinyl cyanide 0-8
Above-mentioned monomer consumption is considered as 100 parts;
PH value buffer reagent: sodium bicarbonate or Sodium phosphate dibasic, 0.2～0.6 part of consumption;
Initiator: Potassium Persulphate or ammonium persulphate, 0.3～1 part of consumption;
80～150 parts of deionized water consumptions.
3. according to claim 1 or 2 described snappiness acetal phenyl propyl soapless copolymerized emulsions, it is characterized in that used raw material monomer vinyl acetate between to for plastic, vinylbenzene, esters of acrylic acid can be unpurified industrial goods.
4. according to claim 1,2 or 3 described snappiness acetal phenyl propyl soapless copolymerized emulsions, it is characterized in that its raw material consists of:
Vinylbenzene 16
Vinyl acetate between to for plastic 15
Butyl acrylate 47
Ethyl propenoate 12
Hydroxyethyl acrylate 4.5
Vinylformic acid 4
N hydroxymethyl acrylamide 1.5
Sodium phosphate dibasic 0.2
Potassium Persulphate 1
Water 100.
5. according to claim 1,2 or 3 described snappiness acetal phenyl propyl soapless copolymerized emulsions, it is characterized in that its raw material consists of:
Vinylbenzene 12
Vinyl acetate between to for plastic 15
Butyl acrylate 59
Vinyl cyanide 8
Vinylformic acid 4
N, N DMAA 2
Sodium bicarbonate 0.6
Potassium Persulphate 0.5
Water 80
6. according to claim 1,2 or 3 described snappiness acetal phenyl propyl soapless copolymerized emulsions, it is characterized in that its raw material consists of:
Vinylbenzene 12
Vinyl acetate between to for plastic 13
Butyl acrylate 60
Methyl methacrylate 7
Propylene glycol monoacrylate 5
Methacrylic acid 1
N hydroxymethyl acrylamide 1.5
Sodium phosphate dibasic 0.3
Ammonium persulphate 0.6
Water 120.
7. according to claim 1,2 or 3 described snappiness acetal phenyl propyl soapless copolymerized emulsions, it is characterized in that its raw material consists of:
Vinylbenzene 15
Vinyl acetate between to for plastic 12
2-EHA 63
Vinyl cyanide 4
Methacrylic acid 3
N, N DMAA 3
Sodium bicarbonate 0.5
Ammonium persulphate 0.3
Water 150.
8. press the preparation method of claim 1,2,3,4,5,6 or 7 described snappiness acetal phenyl propyl soapless copolymerized emulsions, it is characterized in that, in deionized water medium, under the stirring with 80-120 rev/min of speed, be warming up to 60 ℃, disposable adding 70% initiator and buffer agent solution continue to be heated to 80--85 ℃, the parallel dropping mix monomer of difference and the acrylic amide aqueous solution, the dropping time was controlled at 4 hours.Drip after 2 hours, begin to drip the initiator of residue 30% and buffer reagent and mix monomer, amide aqueous solution and drip simultaneously, be incubated 1 hour after adding, wait to cool to below 40 ℃ and filter discharging.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031391087A CN1268657C (en) | 2003-08-13 | 2003-08-13 | High elasticity acetal phenyl propyl soapless copolymerized emulsion and its preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031391087A CN1268657C (en) | 2003-08-13 | 2003-08-13 | High elasticity acetal phenyl propyl soapless copolymerized emulsion and its preparation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1513889A true CN1513889A (en) | 2004-07-21 |
| CN1268657C CN1268657C (en) | 2006-08-09 |
Family
ID=34240154
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB031391087A Expired - Fee Related CN1268657C (en) | 2003-08-13 | 2003-08-13 | High elasticity acetal phenyl propyl soapless copolymerized emulsion and its preparation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1268657C (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101080469B (en) * | 2005-12-16 | 2010-12-22 | Bms有限公司 | Surface hardening composition for preventing flying dust |
| CN102731717A (en) * | 2012-07-18 | 2012-10-17 | 中国海洋石油总公司 | Waterborne dispersion resin containing hydroxyl and preparation method thereof |
| CN102898589A (en) * | 2012-09-11 | 2013-01-30 | 青岛清大联创高新技术有限公司 | Novel environment-friendly high-molecular polymerized emulsion and preparation method thereof |
| CN103773284A (en) * | 2013-12-15 | 2014-05-07 | 江苏黑松林粘合剂厂有限公司 | Weather-resistant water-based adhesive and preparation method thereof |
| CN103980412A (en) * | 2014-05-15 | 2014-08-13 | 中国建筑材料科学研究总院 | Method for preparing high-efficiency molecular sieve desiccant with nanometer core-shell structure |
| CN105732875A (en) * | 2016-02-28 | 2016-07-06 | 吉林建筑大学 | Multifunctional quaternary soap-free vinyl acetate-acrylic emulsion and preparation method thereof |
| CN114832789A (en) * | 2022-03-23 | 2022-08-02 | 江门市新会区中盛生物科技有限公司 | Method for removing polymerization inhibitor in acrylic acid by replacing activated carbon adsorption and adsorbent |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101280163B (en) * | 2007-08-22 | 2010-05-26 | 浙江传化股份有限公司 | Nonwoven cloth adhesive and preparation thereof |
-
2003
- 2003-08-13 CN CNB031391087A patent/CN1268657C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101080469B (en) * | 2005-12-16 | 2010-12-22 | Bms有限公司 | Surface hardening composition for preventing flying dust |
| CN102731717A (en) * | 2012-07-18 | 2012-10-17 | 中国海洋石油总公司 | Waterborne dispersion resin containing hydroxyl and preparation method thereof |
| CN102898589A (en) * | 2012-09-11 | 2013-01-30 | 青岛清大联创高新技术有限公司 | Novel environment-friendly high-molecular polymerized emulsion and preparation method thereof |
| CN103773284A (en) * | 2013-12-15 | 2014-05-07 | 江苏黑松林粘合剂厂有限公司 | Weather-resistant water-based adhesive and preparation method thereof |
| CN103773284B (en) * | 2013-12-15 | 2015-07-08 | 江苏黑松林粘合剂厂有限公司 | Weather-resistant water-based adhesive and preparation method thereof |
| CN103980412A (en) * | 2014-05-15 | 2014-08-13 | 中国建筑材料科学研究总院 | Method for preparing high-efficiency molecular sieve desiccant with nanometer core-shell structure |
| CN105732875A (en) * | 2016-02-28 | 2016-07-06 | 吉林建筑大学 | Multifunctional quaternary soap-free vinyl acetate-acrylic emulsion and preparation method thereof |
| CN114832789A (en) * | 2022-03-23 | 2022-08-02 | 江门市新会区中盛生物科技有限公司 | Method for removing polymerization inhibitor in acrylic acid by replacing activated carbon adsorption and adsorbent |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1268657C (en) | 2006-08-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1293159C (en) | Method for preparing starch glue for lumber | |
| CN1918254A (en) | Acrylic pressure-sensitive adhesive composition for polarizing film | |
| CN1124286C (en) | Process for producing vinyl acetate resin emulsion and water-based adhesive | |
| CN102153971B (en) | Waterborne aluminium foil adhesive and preparation method thereof | |
| CN100415845C (en) | Preparation process and application of water resistant starch-base timber adhesive | |
| JP6463737B2 (en) | Production of pressure-sensitive adhesive dispersions by multi-stage emulsion polymerization for the application of protective films | |
| CN1116351C (en) | Aqueous solution and its producing method | |
| CN102516904B (en) | Single-component water-based adhesive for evaporative cooling wet curtain and preparation method thereof | |
| CN1268657C (en) | High elasticity acetal phenyl propyl soapless copolymerized emulsion and its preparation | |
| US20120070656A1 (en) | Anti-reflective coatings | |
| CN1957050A (en) | Acrylic pressure sensitive adhesive having antistatic property | |
| CN102140320A (en) | Water-based polyacrylic emulsion laminating adhesive and preparation method thereof | |
| CN1730592A (en) | Composite adhesive for soft wrapper and its preparation method | |
| CN1903898A (en) | Siloxane containing water soluble polymer emulsion and redispersible emulsion powder and its preparation method | |
| CN111285962A (en) | Water-based environment-friendly acrylic emulsion pressure-sensitive adhesive for protective film and preparation method thereof | |
| CN1145051A (en) | Repulpable splicing tape | |
| CN1285382A (en) | Composition of composite crosslinking type aqueous compound film adhesive and preparation process thereof | |
| CN1246351C (en) | Nano macromolecule microball of epoxy function type cross-linked nucleocapsid structure and preparation process thereof | |
| CN1472268A (en) | Lyophilic high-molecular antifogging coating and preparing method thereof | |
| CN1823150A (en) | Water-whitening resistant latex emulsion pressure sensitive adhesive and its production | |
| CN104059192B (en) | A kind of non-commixed type polyacrylic ester water swelling rubber and mass polymerization preparation method thereof | |
| CN1268658C (en) | Water dispersion type emulsion of crylic acid, preparation method and usage | |
| CN1807471A (en) | Vinyl acetate based high viscosity latex preparation method | |
| CN1903930A (en) | Flexible acrylic acid waste polyurethane water composite joint filling material and its preparation method | |
| CN1063455C (en) | Dispersing liquid used in pressure sensitive adhesive |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Assignee: Shijiazhuang Paint Factory Assignor: Hebei University of Science and Technology Contract fulfillment period: 2009.7.22 to 2015.7.22 contract change Contract record no.: 2009130000102 Denomination of invention: High elasticity acetal phenyl propyl soapless copolymerized emulsion and its preparation Granted publication date: 20060809 License type: Exclusive license Record date: 2009.8.10 |
|
| LIC | Patent licence contract for exploitation submitted for record |
Free format text: EXCLUSIVE LICENSE; TIME LIMIT OF IMPLEMENTING CONTACT: 2009.7.22 TO 2015.7.22; CHANGE OF CONTRACT Name of requester: SHIJIAZHUANG CITY PAINT FACTORY Effective date: 20090810 |
|
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20060809 Termination date: 20110813 |