CN101402704A - Uses of allyloxy hydroxide sodium dimercaptosulphanate in PVC processing aid - Google Patents
Uses of allyloxy hydroxide sodium dimercaptosulphanate in PVC processing aid Download PDFInfo
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- CN101402704A CN101402704A CNA2008101605576A CN200810160557A CN101402704A CN 101402704 A CN101402704 A CN 101402704A CN A2008101605576 A CNA2008101605576 A CN A2008101605576A CN 200810160557 A CN200810160557 A CN 200810160557A CN 101402704 A CN101402704 A CN 101402704A
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Abstract
The invention provides allyloxy hydroxypropyl sodium sulfonate as an emulsifier for a processing aid ACR emulsion polymerization reaction. The allyloxy hydroxypropyl sodium sulfonate is taken as a reactive emulsifier, which can carry out polymerization reaction with the monomer of raw material during the processing aid ACR emulsion polymerization reaction process. The adoption of the reactive emulsifier has following advantages: as the reactive emulsifier has polymerization activity, the carbon-carbon double bond functional group can participate in the emulsion polymerization reaction, the reaction emulsifier not only has the function of a conventional emulsifier but also can be bonded to the surface of polymer particles by a manner of covalent bond and become part of the polymer; therefore, after polymerization, the emulsifier molecules are bonded to the surface of emulsoid particles by a manner of more stable covalent bond and the processing aid ACR emulsion prepared has better stability. Besides, the degree of adhering to a spray tower during the drying process of the processing aid ACR emulsion is reduced and spray drying rate is improved. The degree of fusion between the processing aid ACR and a PVC resin is not affected and the plasticizing time of PVC can be shortened to some extent.
Description
Technical field
The invention belongs to PVC processing aid field, the application of particularly a kind of reactive emulsifier in the PVC processing aid.
Background technology
Along with the aggravation of processing aid ACR market competition, manufacturing enterprise improves production technique all in the optimization of C of going into overdrive, and makes every effort to enhance productivity, and reduces production costs.Processing aid ACR generally adopts emulsion polymerization technique, and emulsifying agent is general to adopt not non-reactive emulsifier with monomer reaction.In the ACR emulsion polymerization process, the existence of emulsifying agent is indispensable extremely, it is one of necessary raw material of process for processing auxiliary agent A CR high molecular polymer, but after the intermediate emulsion makes Powdered finished product through drying process with atomizing, emulsifying agent becomes impurity on the contrary in finished product, the existence of emulsifying agent is for processing aid ACR, shortcoming has: the stability that influences intermediate A CR emulsion, influence the degrees of fusion between processing aid and the polyvinyl chloride resin, influence the plasticizing effect of processing aid to PVC, influence and be stained with the wall performance in the PVC extrusion, increase the weight of the severity of processing aid ACR sticking tower in spray tower, reduce spraying drying speed, increased the labour intensity that the workman clears up spray tower.
Summary of the invention
Technical problem to be solved by this invention provides a kind of reactive emulsifier, and this reactive emulsifier can carry out polyreaction with starting monomer in PVC processing aid ACR emulsion polymerization process.
For achieving the above object, the invention provides the emulsifying agent of allyloxy hydroxide sodium dimercaptosulphanatein as processing aid ACR emulsion polymerization, it can carry out polyreaction as a kind of reactive emulsifier with starting monomer in processing aid ACR emulsion polymerization process.Because of there is carbon-carbon double bond functional group in allyloxy hydroxide sodium dimercaptosulphanatein,, become the part of polymkeric substance with the polymerization single polymerization monomer reaction of processing aid ACR.
The production process of processing aid ACR of the present invention is: add soft water in reactor; one section emulsifying agent (allyloxy hydroxide sodium dimercaptosulphanatein); one section monomer (methyl methacrylate and butyl acrylate or ethyl propenoate; methyl methacrylate and butyl acrylate); the capping still; heat up; logical nitrogen protection; when being elevated to 75 ℃, temperature adds initiator (Potassium Persulphate or ammonium persulphate) initiation reaction; after the reaction beginning; temperature raises; open cooling water management temperature of reaction below 88 ℃; after one section reaction finishes; when dropping to 75 ℃, temperature adds two sections emulsifying agents; two sections monomers start second-stage reaction.After reaction began, temperature rose, and opened cooling water management temperature of reaction and was no more than 85 ℃, and cooling obtained the ACR emulsion after reaction finished.The spray-dried then finished product ACR powder that obtains.
The basic production of above-mentioned reaction process, the just difference of emulsifying agent employing with existing processing aid ACR.General mix monomer is made up of ethyl propenoate, methyl methacrylate and butyl acrylate, and its part by weight is: butyl acrylate accounts for 95%-25%, and ethyl propenoate, methyl methacrylate account for remaining 5%-75% with the arbitrary proportion mixing.If monomer adopts methyl methacrylate and butyl acrylate, butyl acrylate accounts for 95%-25%, and methyl methacrylate accounts for remaining 5%-75%.Polyreaction is general divides two sections and carries out, and every section monomer consumption and emulsifying agent consumption account for 50%.Emulsifying agent (though this emulsifying agent participates in polyreaction, not as polymerization single polymerization monomer, still being considered as emulsifying agent) is generally 0.1～0.5% (wt) of polymerization single polymerization monomer total amount, and initiator is generally 0.2～4% (wt) of polymerization single polymerization monomer total amount.
The processing aid ACR that adopts the present invention's preparation is as the PVC processing aid, and usage quantity is identical with the processing aid ACR consumption that adopts conventional non-reactive emulsifier to prepare, and is 100 parts in the weight of PVC, adds 3～5 parts.Do not influence the application of other kind analog assistant of polyvinyl chloride resin.
The production of PVC processing aid ACR, the non-reactive emulsifier of employed routine in the mode of physical adsorption attached to the emulsion particle surface, thereby realize the stability of emulsion system.What this conventional emulsifier molecule was subjected to external environment easily influences the generation desorb, and the result causes emulsion particle collision cohesion, causes product rejection.And adopt reactive emulsifier tangible advantage to be arranged than conventional emulsifier, because it has polymerization activity, its carbon-carbon double bond functional group can participate in emulsion polymerization, except playing conventional emulsifier, can also be bonded to the polymer beads sub-surface in the mode of covalent linkage, become the part of polymkeric substance, after polymerization finishes like this, the emulsifying agent molecule is combined on the emulsion particle surface with more stable covalent, and prepared processing aid ACR emulsion has better stability.Reduced processing aid ACR glues tower in spray tower in drying process degree, improved spraying drying speed, reduced the labour intensity (being reduced to for three times twice weekly) that the workman clears up spray tower by original cleaning weekly.The processing aid ACR and the degrees of fusion between the polyvinyl chloride resin that make are unaffected, can shorten the fusion time of PVC to a certain extent.
Embodiment
Embodiment one:
In reactor, add soft water 800kg; one section emulsifying agent allyloxy hydroxide sodium dimercaptosulphanatein 1.1kg; one section monomer (ethyl propenoate 220kg; methyl methacrylate 220kg and butyl acrylate 660kg); the capping still; heat up; logical nitrogen protection; when being elevated to 75 ℃, temperature adds initiator (Potassium Persulphate or ammonium persulphate 8.8kg) initiation reaction; after the reaction beginning; temperature raises; open cooling water management temperature of reaction below 88 ℃; after one section reaction finishes; when dropping to 75 ℃, temperature adds two sections emulsifying agent allyloxy hydroxide sodium dimercaptosulphanatein 1.1kg; two sections monomer (ethyl propenoate 220kg; methyl methacrylate 220kg and butyl acrylate 660kg), start second-stage reaction.After reaction began, temperature rose, and opened cooling water management temperature of reaction and was no more than 85 ℃, and cooling after reaction finishes obtains the ACR emulsion.The spray-dried then finished product processing aid ACR powder that obtains.
Embodiment two:
In reactor, add soft water 800kg; one section emulsifying agent allyloxy hydroxide sodium dimercaptosulphanatein 3.3kg; one section monomer (ethyl propenoate 220kg; methyl methacrylate 220kg and butyl acrylate 660kg); the capping still; heat up; logical nitrogen protection; when being elevated to 75 ℃, temperature adds initiator (Potassium Persulphate or ammonium persulphate 10kg) initiation reaction; after the reaction beginning; temperature raises; open cooling water management temperature of reaction below 88 ℃; after one section reaction finishes; when dropping to 75 ℃, temperature adds two sections emulsifying agent allyloxy hydroxide sodium dimercaptosulphanatein 3.3kg; two sections monomer (ethyl propenoate 220kg; methyl methacrylate 220kg and butyl acrylate 660kg), start second-stage reaction.After reaction began, temperature rose, and opened cooling water management temperature of reaction and was no more than 85 ℃, and cooling after reaction finishes obtains the ACR emulsion.The spray-dried then finished product processing aid ACR powder that obtains.
Embodiment three:
In reactor, add soft water 800kg; one section emulsifying agent allyloxy hydroxide sodium dimercaptosulphanatein 5.5kg; one section monomer (ethyl propenoate 220kg; methyl methacrylate 220kg and butyl acrylate 660kg); the capping still; heat up; logical nitrogen protection; when being elevated to 75 ℃, temperature adds initiator (Potassium Persulphate or ammonium persulphate 18kg) initiation reaction; after the reaction beginning; temperature raises; open cooling water management temperature of reaction below 88 ℃; after one section reaction finishes; when dropping to 75 ℃, temperature adds two sections emulsifying agent allyloxy hydroxide sodium dimercaptosulphanatein 5.5kg; two sections monomer (ethyl propenoate 220kg; methyl methacrylate 220kg and butyl acrylate 660kg), start second-stage reaction.After reaction began, temperature rose, and opened cooling water management temperature of reaction and was no more than 85 ℃, and cooling after reaction finishes obtains the ACR emulsion.The spray-dried then finished product processing aid ACR powder that obtains.
Embodiment four:
In reactor, add soft water 800kg; one section emulsifying agent allyloxy hydroxide sodium dimercaptosulphanatein 5.5kg; one section monomer (ethyl propenoate 110kg; methyl methacrylate 550kg and butyl acrylate 440kg); the capping still; heat up; logical nitrogen protection; when being elevated to 75 ℃, temperature adds initiator (Potassium Persulphate or ammonium persulphate 22kg) initiation reaction; after the reaction beginning; temperature raises; open cooling water management temperature of reaction below 88 ℃; after one section reaction finishes; when dropping to 75 ℃, temperature adds two sections emulsifying agent allyloxy hydroxide sodium dimercaptosulphanatein 5.5kg; two sections monomer (ethyl propenoate 110kg; methyl methacrylate 550kg and butyl acrylate 440kg), start second-stage reaction.After reaction began, temperature rose, and opened cooling water management temperature of reaction and was no more than 85 ℃, and cooling after reaction finishes obtains the ACR emulsion.The spray-dried then finished product processing aid ACR powder that obtains.
Embodiment five:
In reactor, add soft water 800kg; one section emulsifying agent allyloxy hydroxide sodium dimercaptosulphanatein 3.3kg; one section monomer (methyl methacrylate 550kg and butyl acrylate 550kg); the capping still; heat up; logical nitrogen protection; when being elevated to 75 ℃, temperature adds initiator (Potassium Persulphate or ammonium persulphate 20kg) initiation reaction; after the reaction beginning; temperature raises; open cooling water management temperature of reaction below 88 ℃; after one section reaction finishes; when dropping to 75 ℃, temperature adds two sections emulsifying agent allyloxy hydroxide sodium dimercaptosulphanatein 3.3kg; two sections monomers (methyl methacrylate 550kg and butyl acrylate 550kg) start second-stage reaction.After reaction began, temperature rose, and opened cooling water management temperature of reaction and was no more than 85 ℃, and cooling after reaction finishes obtains the ACR emulsion.The spray-dried then finished product processing aid ACR powder that obtains.
The polyvinyl chloride (PVC) RESINS test formulations:
The processing aid ACR that the foregoing description 1～5 is made is by following described formulated polyvinyl chloride material.
100 parts of polyvinyl chloride
3 parts of embodiment gained processing aid ACR
5 parts in lime carbonate
3 parts of tribasic lead sulfates
2 parts of dibasic Lead Phosphites
0.6 part of calcium stearate
0.8 part of lead stearate
0.15 part of polyethylene wax
0.1 part of stearic acid
4 parts of titanium dioxide
Take by weighing each raw material and mix according to described prescription, use homogenizer to carry out high-speed mixing, temperature stops to stir blowing when being elevated to 120 ℃, divides naturally cooling cooling on cooling table, obtains test and uses the polyvinyl chloride compound, measures its fusion time.
Test result sees the following form 1.
| The polyvinyl chloride material | Fusion time, second |
| Embodiment one | 31 |
| Embodiment two | 28 |
| Embodiment three | 27 |
| Embodiment four | 27 |
| Embodiment five | 29 |
| Comparative Examples | 36 |
Annotate: the polyvinyl chloride material that Comparative Examples is prepared for the processing aid ACR that adopts existing non-reactive emulsifier (sodium lauryl sulphate) to make.
Adopt the technical indicator of the ACR that non-reactive emulsifier (sodium lauryl sulphate) obtains and adopt the technical indicator of the ACR that reactive emulsifier obtains, as following table 2:
| Technical indicator | Adopt reactive emulsifier | Adopt non-reactive emulsifier |
| Outward appearance | The white free-flowing powder | The white free-flowing powder |
| Apparent density (g/cm 3) | 3.58 | 3.53 |
| Granularity (40 mesh standard sieve percent of pass) | 98.3 | 98.0 |
| Fugitive constituent (%) | 0.8 | 0.7 |
In the table data as can be seen the old and new's technology products obtained therefrom aspect physical and chemical indexes, do not have difference substantially.
The stability test of centrifugal determination processing aid ACR emulsion:
With processing aid ACR emulsion to be measured, get 100mL respectively, put into whizzer, processing aid ACR emulsion needs 10000 rev/mins of high speed centrifugation 20min, takes out emulsion, and the visual observation emulsion state shakes then gently, and the observation emulsion is mobile as following table 3:
The processing aid ACR emulsion and the Comparative Examples (the processing aid ACR emulsion that adopts existing non-reactive emulsifier sodium lauryl sulphate to make) that adopt embodiment 1～5 to make are carried out spray drying experiment respectively.All in 1 ton of emulsion spraying drying time.See the following form 4:
| Processing aid ACR emulsion | The spraying drying time, minute |
| Embodiment one | 114 |
| Embodiment two | 106 |
| Embodiment three | 97 |
| Embodiment four | 98 |
| Embodiment five | 105 |
| Comparative Examples | 131 |
Claims (1)
1, allyloxy hydroxide sodium dimercaptosulphanatein is as the emulsifying agent of PVC processing aid ACR emulsion polymerization.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008101605576A CN101402704A (en) | 2008-11-14 | 2008-11-14 | Uses of allyloxy hydroxide sodium dimercaptosulphanate in PVC processing aid |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008101605576A CN101402704A (en) | 2008-11-14 | 2008-11-14 | Uses of allyloxy hydroxide sodium dimercaptosulphanate in PVC processing aid |
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| Publication Number | Publication Date |
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| CN101402704A true CN101402704A (en) | 2009-04-08 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110325563A (en) * | 2017-02-24 | 2019-10-11 | 关西涂料株式会社 | Polymer composition and its manufacturing method containing modified chlorinated polyolefin |
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2008
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110325563A (en) * | 2017-02-24 | 2019-10-11 | 关西涂料株式会社 | Polymer composition and its manufacturing method containing modified chlorinated polyolefin |
| CN110325563B (en) * | 2017-02-24 | 2022-01-11 | 关西涂料株式会社 | Polymer composition containing modified chlorinated polyolefin and method for producing same |
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Open date: 20090408 |