GB2086919A - Vinyl Chloride Polymerization - Google Patents
Vinyl Chloride Polymerization Download PDFInfo
- Publication number
- GB2086919A GB2086919A GB8132985A GB8132985A GB2086919A GB 2086919 A GB2086919 A GB 2086919A GB 8132985 A GB8132985 A GB 8132985A GB 8132985 A GB8132985 A GB 8132985A GB 2086919 A GB2086919 A GB 2086919A
- Authority
- GB
- United Kingdom
- Prior art keywords
- polymerization
- mass
- vinyl chloride
- process according
- esters
- 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.)
- Withdrawn
Links
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 19
- 229920000642 polymer Polymers 0.000 claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 239000003999 initiator Substances 0.000 claims abstract description 9
- 239000000178 monomer Substances 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003381 stabilizer Substances 0.000 claims abstract description 6
- 239000000725 suspension Substances 0.000 claims abstract description 6
- 239000012736 aqueous medium Substances 0.000 claims abstract description 5
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 5
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- 238000010526 radical polymerization reaction Methods 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 22
- 150000002148 esters Chemical class 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 5
- -1 n-octyl Chemical group 0.000 claims description 5
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 4
- 239000000194 fatty acid Substances 0.000 claims description 4
- 229930195729 fatty acid Natural products 0.000 claims description 4
- 150000004665 fatty acids Chemical class 0.000 claims description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 2
- 150000007513 acids Chemical class 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 239000008346 aqueous phase Substances 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 239000012188 paraffin wax Substances 0.000 claims description 2
- 239000012966 redox initiator Substances 0.000 claims description 2
- 239000002245 particle Substances 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 239000012530 fluid Substances 0.000 abstract 1
- 229910002567 K2S2O8 Inorganic materials 0.000 description 12
- 235000019394 potassium persulphate Nutrition 0.000 description 12
- 229910004879 Na2S2O5 Inorganic materials 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 8
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 8
- 235000010262 sodium metabisulphite Nutrition 0.000 description 8
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- 238000010557 suspension polymerization reaction Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000006057 Non-nutritive feed additive Substances 0.000 description 2
- 239000004902 Softening Agent Substances 0.000 description 2
- 238000012662 bulk polymerization Methods 0.000 description 2
- 241000237074 Centris Species 0.000 description 1
- 239000004803 Di-2ethylhexylphthalate Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical class OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- 150000004764 thiosulfuric acid derivatives Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F14/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F14/02—Monomers containing chlorine
- C08F14/04—Monomers containing two carbon atoms
- C08F14/06—Vinyl chloride
Abstract
Pearl polymerizates are produced by radical polymerization of vinyl chloride and monomer mixtures in an aqueous medium by use of water soluble initiators without suspension stabilizers and emulsifiers. Initial polymerization mixture may be dissolved in specific organic solvents and VC may be replenished during reaction. The VC polymers obtained are pearl-shaped VC polymerizates of uniform particle size, high porosity, fluid stable and shape- retentive under heat.
Description
SPECIFICATION
Process for Production of Vinyl Chloride Polymers
The invention relates to a process for producing vinyl chloride polymers in the form of pearl polymerizates by radical polymerization of vinyl chloride (VC) and monomer mixtures containing mostly
VC in an aqueous medium and at temperatures of between 273 and 353 K, the polymers being suitable both for hard and soft processing.
Porous VC polymerizates can be produced by suspension polymerization processes wherein the actual polymerization takes place by oil-soluble radical initiators, and in which the polymer drops are stabilized by the addition of water-soluble suspension stabilizers (0.05 to 0. 19/0 based on the mass of the VC).
The polymerization products with Fikentsch K values of between 50 and 70 are produced in the form of powder, generally with a particle diameter of between 50 and 200 gem and a bulk density of between 0.48 and 0.58 g/cm3. Plasticization of the polymerizates, which is important for their processability, is decisively influenced by the proportion represented by and the specific characteristics of the protective colloid film formed in the presence of water-soluble suspension stabilizers, which film is also termed a pericellular skin.
The suspension polymerization methods most frequently employed provide, despite the formation of pericellular skins, polymers with processing characteristics usually sufficient for usual applications of PVC. The suspension processes require, however, particularly due to the conflict between porosity (absorption of softening agent) and compactness of the polymer grain (bulk density), special suspens:on stabilization systems which are usually very sensitive and to incur considerable costs.
In mass polymerization technology basically similar processes take place as occur within the drop in VC suspension polymerization and the same primary particle structure or globule structure occurs (R.
Salovey etc., Polym. Engng. Sci. 14 (1974) 2, 120-123), porous polymer grains are produced without an pericellular skins, and these absorb processing aids and additives satisfactorily and evenly IH. Huber and W. D. Mitterberger, Kunststoffe 63 (1973) 11,726--728).
By using suitable dispersing agent systems (German Specifications 2610021 and 2702771, U.S.
Pat 3630976) or adding special porosity modifiers (German Specifications 2603025 and 2701971,
U.S. Pat.3642744) highly porous VC polymers with limited bulk density (generally < 0.56 g/cm3) are obtained in suspension polymerization. On the other hand, various technical and technological measures (French Patents 1357736 and 1522403, German specification 2002380) provide VC polymerizates of high bulk density (~0.60 g/cm3), although the porosity of these polymerizates is very limited being a compact PVC with low softening anent absorption rates.
Furthermore, mass polymerization processes are limited in their uses owing to the difficulty of dissipating the heat of reaction as there is no water carrier phase.
In the emuision polymerization process, VC is mainly polymerizated in the soap micells, in the presence of emulsifiers and water-soluble initiators:
(D. C. Blackley, Emulsion Polymerization Theory and Practice, Appl. Sci. Pub. Ltd., London (1975) pp. 7-23).
The resulting emulsion polymerizates can have a very high emulsifier content and are mainly used for paste processing.
With conventional VC polymerization methods, mainly arising from three basic processes, it is not possible to produce pearl-shaped PVC with good properties for its use and application.
It is an object of the invention to produce pearl shaped porous vinyl chloride polymers of high bulk density on the basis of a simplified polymerization technique.
The invention seeks to develop a process for production of pearl-shaped porous polymerizates by radical polymerization of VC or monomer mixtures containing mostly VC, the reaction being performed in an aqueous medium using known polymerization initiators, in a temperature range of 273--3530 K, preferably 300--3400 K.
According to this invention there is provided a process for the production of vinyl chloride polymers in the form of pearl polymerizates by the radical polymerization of vinyl chloride or monomer mixtures containing mostly VC, in an aqueous medium and at temperatures of between 273 and 3530
K, wherein the VC, in a proportion of 5 40% in relation to the mass of the water, is distributed by stirring in the aqueous phase 20-100 pts. by mass of VC to 100 pts by mass of water being added, and polymerized, by use of water-soluble initiators in the absence of suspension stabilizers and emulsifiers, to a solid-matter content of between 1 5 and 50% by mass.
Water-soluble redox initiators, such as systems consisting of K2S208, (NH4)2S203, (hydrogen-) sulphites, dithionites, thiosulphates, alkyl mercaptans or a cetoacetic ester and the like, have proved to be advantageous polymerization initiators.
By using these redox systems and peroxidisulphates alone, VC polymerizates are obtained at polymerization temperatures of between 300 and 3400 K, within a widely variable range of Fikentsch values, with particularly high K values, in a range of 55-90.
In addition it is possible, for the aqueous initiator solution to use inert organic solvents, particularly paraffin hydrocarbons with 6-12 carbon atoms, esters of fatty acids of higher molecular weight or esters of aliphatic and aromatic dicarbonic acids, preferably n-octyl- and 2-ethyl-hexylesters of fatty acids with 1 1 8 carbon atoms, in addition to esters of adipic and phthalic acid which are not usually separated from the resulting polymer product, in view of the intended application.
Other known processing aids, particularly stabilizers, softeners and lubricants, may be added to the preliminary polymerization mixture before, or during or also after the polymerization.
The resulting VC polymers have a very uniform structure with uniform globules and without any pericellular skins and also uniform appearance being pearl-shaped particles with an almost constant diameter within the range 0.2-5 mm.
The polymerizates are characterized both by a high degree of porosity (absorption of softening agent and speed of the said absorption) and by high bulk density and considerable fluidity, in addition to high stability when subjected to heat and ability to retain their shape under heat in the corresponding K value range.
Example
In a rinsed oxygen-free polymerization vessel equipped with a stirring device, 100 pts, by mass of water, in which 0.05 pts. by mass of K2S20" and 0.02 pts. by mass of Na2S205 are dissolved, and 40 pts.
by mass of VC are added at room temperature. While stirring, the initial polymerization mixture is heated up to a temperature of 3130 K (Tpm) and polymerized within a total period of 3 hrs while the Tpm is maintained and the VC replenished from a monomer storage vessel in a proportion of 10 pts. by mass per 30 min.
The vessel is then relieved of pressure and rinsed with inert nitrogen. This produces a total of 52 pts. by mass of PVC with the following polymerization parameters:
Fikentach K value: 83
Particle diameter: 0.81--0.85 mm
Bulk density: 0.58 g/cm3
Fluidity (TGL 1 622 1): 21 gis Softener absorption centrifuge: 22% by mass
di-2-ethyl hexyl
phthalate (DOP)
Softener absorption speed: (Grease spot method, TGL 28475): 0-5 min
Heat stability (furnace test, TGL 28475): 70 min
Vicate softening temperature (TGL 17274,49 N superimposed weight in air): 365 K
Residual monomer content of PVC: 1 ppm VC
The above example produces the VC polymerizates given in Table I with the variation of the Tpm or of the polymerization initiator (the K2S20JNa2SO05 system in addition to the pure peroxidisulphate) and of the polymerization conditions (quantitative ratio: initial and replenished monomer as a function of the polymerization time in hours).
Columns 6 to 9 indicate, as the important polymer characteristics, the Fikentsch K value, the bulk density (b.d.), the percentage of softener absorption by means of the centrifuge and the vicate softening temperature (VSP).
In addition, the pearl-shaped polymer products, the particle diameter being preferably variable between 0.5 and 2 mm, show high fluidity ( > 1 5 g/s according to TGL 160-221), softener absorption speed (generally 0--5 min. according to TGL 28475) and heat stability (between 30 and=50 min.
according to TGL 28475) as well as a low residual VC content, so that no additional demonomerization stage is required.
In Ex. 9 and 11,20 pts, by mass of di-n-ethyl hexyl adipate have been added, while 30 pts. by mass of n-heptane have been added in Ex. 10 and 12, to the initial polymerization mixture. This results in a product of considerably uniform "pearl size".
Table 1
Monomer mass:
Pts/mass Waterto 100 pts/mass abs. by of water centri
Initial Additional Pm time: Tpm: Bulk fuge VSP:
No. Initiator (%) mixture supply hrs: K K Values density: (%DOP): K: 1 0.05 K2S2O8 40 60 3.0 313 85 0.58 28 365 0.02 Na2S2O5 2 0.05 K2S2O8 50 40 2.0 318 79 0.61 25 363 0.02 Na2S2O5 3 0.05 K2S2O8 70 - 2.0 318 78 0.57 23 360 0.02 Na2S2O5 4 0.05 K2S2O8 40 80 3.5 323 75 0.57 18 364 5 0.08 K2S2O8 50 50 2.0 335 66 0.55 12 363 6 0.05 K2S2O8 40 40 2.0 303 87 0.61 33 360 0.02 Na2S2O5 7 0.05 K2S2O8 40 60 3.0 318 81 0.57 23 362 0.02 Na2S2O5 8 0.05 K2S2O8 40 60 3.0 318 80 0.58 24 365 0.02 Na2S2O5 9 0.05 K2S2O8 20 60 2.5 313 85 0.64 29 360 0.02 Na2S2O5 10 0.05 K2S2O8 20 80 3.5 313 86 0.65 27 362 0.02 Na2S2O5 11 0.07 K2S2O8 20 40 1.5 333 65 0.62 10 359 12 0.05 K2S2O8 20 60 2.0 328 70 0.64 19 359
Claims (10)
1. Process for the production of vinyl chloride polymers in the form of pearl polymerizates by the radical polymerization of vinyl chloride or monomer mixtures containing mostly VC, in an aqueous medium and at temperatures of between 273 and 3530 K, wherein the VC, in a proportion of 5 40% in relation to the mass of the water, is distributed by stirring in the aqueous phase, 20--100 pts. by mass of VC to 100 pts by mass of water being added, and polymerized, by use of water-soluble initiators in the absence of suspension stabilizers and emulsifiers, to a solid-matter content of between 15 and 50% by mass.
2. Process according to Claim 1, wherein the polymerization occurs at temperatures of between 300 and 3400 K.
3. Process according to Claim 1 or 2, wherein inert organic solvents are added to the VC.
4. Process according to Claim 3, wherein the organic solvents are selected from paraffin hydrocarbons with 6-12 carbon atoms, esters of fatty acids of higher molecular weight, esters of aliphatic and aromatic dicarbonic acids and esters of adipic and phthalic acid.
5. Process according to Claim 4, wherein the organic solvent is selected from n-octyl and 2-ethyl hexyl esters of fatty acids with 10 to 18 carbon atoms.
6. Process accoridng to any preceding claim, wherein the initiators are peroxidisulphates or redox initiators.
7. Process according to any preceding claim, wherein the VC is replenished during the course of polymerization.
8. Process according to any preceding claim, wherein the initiator is replenished if necessary during the course of polymerization.
9. A process for the production of vinyl chloride polymers substantially as herein described with reference to the example.
10. A vinyl chloride polymer produced by the method of any of claims 1 to 9.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DD80224938A DD154101A1 (en) | 1980-11-04 | 1980-11-04 | PROCESS FOR THE PREPARATION OF VINYL CHLORIDE POLYMERS |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| GB2086919A true GB2086919A (en) | 1982-05-19 |
Family
ID=5527035
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB8132985A Withdrawn GB2086919A (en) | 1980-11-04 | 1981-11-02 | Vinyl Chloride Polymerization |
Country Status (7)
| Country | Link |
|---|---|
| BE (1) | BE890905A (en) |
| DD (1) | DD154101A1 (en) |
| DE (1) | DE3140722A1 (en) |
| FR (1) | FR2496674A1 (en) |
| GB (1) | GB2086919A (en) |
| IT (1) | IT8149627A0 (en) |
| SE (1) | SE8106499L (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0164883A2 (en) * | 1984-05-07 | 1985-12-18 | Shin-Etsu Chemical Co., Ltd. | A method for the polymerization of a vinylic monomer |
-
1980
- 1980-11-04 DD DD80224938A patent/DD154101A1/en not_active IP Right Cessation
-
1981
- 1981-10-14 DE DE19813140722 patent/DE3140722A1/en not_active Withdrawn
- 1981-10-29 BE BE0/206377A patent/BE890905A/en unknown
- 1981-10-30 FR FR8120459A patent/FR2496674A1/en not_active Withdrawn
- 1981-11-02 GB GB8132985A patent/GB2086919A/en not_active Withdrawn
- 1981-11-03 SE SE8106499A patent/SE8106499L/en not_active Application Discontinuation
- 1981-11-03 IT IT8149627A patent/IT8149627A0/en unknown
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0164883A2 (en) * | 1984-05-07 | 1985-12-18 | Shin-Etsu Chemical Co., Ltd. | A method for the polymerization of a vinylic monomer |
| EP0164883A3 (en) * | 1984-05-07 | 1986-04-16 | Shin-Etsu Chemical Co., Ltd. | A method for the polymerization of a vinylic monomer |
Also Published As
| Publication number | Publication date |
|---|---|
| BE890905A (en) | 1982-02-15 |
| DE3140722A1 (en) | 1982-07-08 |
| IT8149627A0 (en) | 1981-11-03 |
| DD154101A1 (en) | 1982-02-24 |
| SE8106499L (en) | 1982-05-05 |
| FR2496674A1 (en) | 1982-06-25 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| WAP | Application withdrawn, taken to be withdrawn or refused ** after publication under section 16(1) |