HUT67926A - A vinylchloride homo- or copolymer composition ready for processing and its preparation method - Google Patents

Description

Field of the Invention The present invention relates to vinyl chloride for direct processing, in which processability additives, such as stabilizers, lubricants, colorants and strength agents, are added to the polymer in the polymerization reactor.

Polyvinyl chloride / PVC / is a low cost thermoplastic material with many uses. One or more stabilizers, lubricants, pigments and / or modifiers are added to the PVC resin obtained by polymerization to make them suitable for processing. From the point of view of the manufacturers of PVC products, it would be desirable for the polymer they purchase to be as easy to process as possible. Nowadays, this requires the construction of separate mixing plants, either after the polymerization reactor or at the end product manufacturing plant. Research on the addition of additives, in particular stabilizers, during polymerisation, and some publications in the art, is well known.

U.S. Pat. No. 3,862,066 discloses a vinyl chloride suspension polymerization system in which various additives, such as stabilizers, lubricants, pigments and the like, are added to the polymerization reactor at the beginning of polymerization or during polymerization. At the end of the polymerization, an inhibitor to stop the polymerization is added to achieve the desired conversion.

DE 36 30 318 discloses certain polyoxazolines of the type · ♦ · · · · · ént as suspension stabilizers and addition of organic or inorganic zinc compounds as prestabilizers to the polymerization reactor. The final stabilization is then carried out in the usual manner.

In British Patent No. 1,577,030, the additives are added to the polymerization reactor during the bulk polymerization of vinyl chloride. According to the disclosure, conventional additives may be used. The polymerization may also be a two-step polymerization in which the additives are added in the second step. For example, stabilizers, lubricants and processing aids are added to the polymerization mixture.

However, methods known to date, as far as they are known, are clearly unsuccessful on a commercial scale because they are not used in commercial production to obtain a processable polymer. In the experiments leading to the present invention, the addition of polyvinyl chloride additives directly to the polymerization reactor was investigated according to the above-mentioned publications, but it was found that the products were unsuitable for use. Large amounts of scrap product formed that were clumped or adhered to reactor walls. The wax-like lubricants used in the publications interfered with the formation of the dispersion in the reactor.

Surprisingly, it has been found that PVC additives can be added during polymerisation if certain materials are used simultaneously.

- 4 were added to the reactor. Thus, the homo- or copolymer composition of the present invention is characterized in that, at the beginning of the polymerization, during the polymerization or at the end of the polymerization, 0.01 to 50% by weight of the liquid olefin oligomer and / or ethylene-olefin copolymer or olefin a terpolymer is added to the polymerization reactor.

The liquid olefin oligomer may be a dimer, a trimer, a tetramer, a pentamer or a hexamer of α-olefins or internal olefins (C 4 -C 30) or mixtures thereof, with carbon chains of from 20 to 100 carbon atoms. The oligomer may have double bonds or be hydrogenated.

If desired, a liquid polymer may be used which is an elastomeric ethylene-propylene copolymer in which, for example, dicyclopentadiene or ethylidene-norbornene are used as the thermomer. The liquid polymer may be used in addition to or instead of the oligomer. The choice of oligomer and / or liquid polymer to be used will depend on the desired end product. The addition of the liquid oligomer and / or polymer to the polymerization reactor thus allows the addition of other additives at the beginning or during the polymerization to produce a ready-to-process polymer.

The ready-to-process PVC polymers of the present invention can be used for the same products as those made by conventional polymerization and mixing techniques. They can be processed, for example, by extrusion, injection molding, blow molding or calendering, and produce various products such as pipes, pipe fittings, sheets, molds and bottles.

The additives used are the same as those used in the preparation of conventional mixtures. As stabilizing agents, lead compounds such as lead sulphate, phosphite, carbonate or talate or barium / zinc, calcium / zinc or tin compounds can be used. Lead, calcium or zinc stearates, epoxidized soybean oils, epoxidized linseed oils or epoxidized fatty acid esters may be used as co-stabilizers.

Suitable fillers are, for example, calcium carbonates, kaolin, silicon oxide or aluminum hydroxide.

Suitable flame retardants include antimony trioxide, zinc borate, zinc oxide or aluminum hydroxide.

Examples of external lubricants are lead, calcium or zinc stearates, fatty acid esters, alcohols or amides, waxes or esters of montanic acid, paraffin, hydrocarbon or polyethylene waxes.

Suitable coloring agents are carbon black, titanium dioxide, various organic and inorganic pigments.

As a processing aid, for example, a poly (methyl methacrylate) and a strength enhancing agent may be used separately.

Various polymers such as acrylonitrile-butadiene-styrene (ABS), methacrylate-butadiene-styrene (MBS), chlorinated polyethylene (CPE), ethylene-vinyl acetate (EVA) or various acrylate plastic polymers.

Polymerization is carried out in a manner similar to conventional PVC production by conventional slurry polymerization. The vinyl chloride is dispersed in water using, for example, polyvinyl alcohol or cellulose derivatives as suspending agents. The polymerization initiator is an organic peroxide soluble in the monomer. Depending on the product, the polymerization temperature is typically 50-70 ° C and the pressure is accordingly 7-12 bar. The polymerization time is generally 4-8 hours. The length of the polymer chain is almost entirely determined by temperature. In the final step of the polymerization reaction, the polymerization pressure begins to decrease. After the pressure has dropped to the desired value, the batch is transferred to a degassing or stripping vessel where the non-polymerized monomer is recovered and recycled. After stripping, the PVC-water mixture is dried, whereby a portion of the water is mechanically separated, the residue is removed by heat and the product is finally sieved.

The polymerization of the present invention is fundamentally different from conventional polymerization in that one or more of the oligomer and / or liquid polymer and additives that are usually added separately after the polymerization are present before, during or after the polymerization.

- Step 7 is added to the polymerization reactor.

The polymerization process of vinyl chloride according to the present invention provides several advantages over the known process. If the additives are added already during the polymerization step, the homogeneous distribution of the additives is improved as compared to the conventional blend formulation, in which the additives are dry blended with the polymer prior to processing. The additives may be added to the polymerization reactor in the form of an aqueous solution or suspension, thus avoiding the dust formation problems that arise with a conventional mixing process.

The polymerization time is reduced because the degree of polymerization increases at high conversions due to the sudden drop in pressure and a higher conversion rate is achieved.

Stripping conditions are more difficult to maintain in a batch stripping apparatus because the heat stabilizers were added to the polymer prior to stripping. As a result, monomer emissions to air and wastewater are reduced and raw material balance is improved. Discoloration and thermal decomposition of the polymer during stripping is completely avoided.

The efficiency of the drying step can be improved by using a higher inlet temperature and a greater temperature difference. Improved thermal efficiency reduces energy consumption. Thermal decomposition can be eliminated during drying even more than 100 9z • 4 · ♦ ··

- 8, since the heat stabilizers were added during the polymerization.

The screening step is more efficient because, due to the metal-containing additives, static electricity is lower and smaller mesh-sized screens can be used.

The final polymer has better flow properties due to its higher density and larger particle size. As a result, powder formation problems in the final polymer are reduced.

If heavy metals such as lead are used for stabilization, their weight percentage can be reduced for better distribution.

Conventional lubricants are most often not needed and the need for lubricants is substantially reduced, which is particularly advantageous from an economic point of view for extrusion and injection molding.

The invention is illustrated by the following non-limiting examples.

The polymerizations were carried out in an autoclave-type polymerization reactor. Standard test methods were used: bulk density according to ISO R 60, viscosity! number determination and K-value determination according to ISO R 174, plasticizer absorption (DOP) determination ISO 4608

- 9 pts.

1-5. example

To the polymerization reactor was added 10 kg of vinyl chloride (VCM) and 15 kg of water. Calcium stearate and lead sulfate or zinc stearate are also added to the reactor as stabilizers. At the beginning and during the polymerization, a dispersant (polyvinyl alcohol) is added. In addition to the dicetyl peroxide carbonate initiator, lauryl peroxide is also used. The oligomer is added at the start of the polymerization. The oligomer used is a hydrogenated decene oligomer, which is composed mainly of a tetramer (C 40) and also contains all trimer (C 30) and pentamer (C 50). The polymerization recipes are the

Table 1 and the results are shown in Table 2.

Table 1

Recipe for polymerization

Example oligo mer Ca stearate Pb-sulfonic f over Zn stearate Inici- ator PVA laurylperoxide First 7.5 5 5 1.1 1.65 0.2 Second 7.5 5 10 1.4 1.65 0.5 Third 5.0 7.5 10 1.3 1.70 0.5 4th 7.5 10 8 1.25 1.75 - 5th 7.5 10 4 1.25 1.75 -

Table 2

Polymerization results

Example Conversion- polymerized Volume- Particle size Porosity FBAR time crowd % minute g / L D5 0, μια. %

First 81.8 249 525 136 22.9 Second 79.9 228 533 136 23.3 Third 79.3 260 577 170 20.2 4th 75.3 220 562 157 23.8 5. 73.7 257 560 170 22.9

6-9. example

10 kg of vinyl chloride (VCM) and 15 kg of water were added to the polymerization reactor. Calcium stearate and lead sulfate are also added to the reactor as stabilizers. At the beginning and during the polymerization, a dispersant (PVA) is added. In addition to the dicetyl peroxide carbonate initiator, an additional catalyst (cumyl peroxy neodecanoate) is also used. The oligomer and / or liquid ethylene-propylene polymer (E-P) is added at the start of the polymerization. The hydrogenated oligo mer tetramer (C40) and pentamer (C50) blend used and the liquid polymer in Examples 6 and 7 are ethylene-pro-pipylene-dicyclopentadiene terpolymer, in Example 8, ethylene-propylene-norbornene terpolymer and in Example 9, an ethylene-propylene copolymer. The polymerization formulas are shown in Table 3 and the results are shown in Table 4.

Table 3

Recipe for polymerization

Example INTACT oligo mer Ca-steroid reap Pb-sulfate Inici- ator PVA assistant Kata catalyst can 6th 7.5 - 7.5 20 1.3 2.05 0.2 7th 7 7.05 10 15 1.3 2.05 0.5 8th 12 - 4 15 1.3 1.85 - 9th 2.1 4.9 5 12 1.5 1.28 -

Table 4

Polymerization results

Example Conversion- polymerized Volume- Particle size Porosity FBAR time crowd % minute g / 1 D50, μπι %

6th 73.4 248 566 167 21.8 7th 71.2 224 558 151 22.76 8th 81.3 418 583 172 19.9 9th 87.8 243 575 170 25.7

• · ····

10-12. example

The plant-sized polymerizations were carried out using conventional polymerization reactors, in the usual manner for the production of PVC, except that an olefin oligomer and / or a liquid ethylene-propylene copolymer and other additives were added during the polymerization. For comparison, a commercially available resin has a K value of 68. The additives used are listed in Table 5 and the results of the resin assay are shown in Table 6.

Table 5

Applied additives

10th example Example 11 Example 12 oligomer (%) 0.8 0.8 0.3 ethylene - propylene copolymer (%) - - 0.7 Ca stearate (%) 1.0 1.0 0.9 Zn stearate (%) 0.8 0.4 - Pb Sulfate (%) - - 1.2 epoxidized soybean oil (%) 3.0 0.8 0.2

• ··

Table 6

resin test

Example 10 Example 11 Example 12 S-116 bulk density (kg / m ³ ) 498 499 556 560 plasticizer ab- 24.0 25.3 24.5 21.0 sorption (DOP) (%) viscosity number 107.4 112.4 114.0 116.0 K-value 65.6 67.0 67.4 67.9 particle size (D50, μιη) 160 166 131 165

Example 13

Extrusion of tubes from the resins of Examples 10 and 11

110 / 3.2 mm tubes were made from the resins using a CM65 twin screw extruder. Conical Snails: 65/120 mm in diameter, 1210 mm in length, operating speed up to 34.4 rpm and total torsion 10.2 kNm.

The tubes are subjected to severe fracture tests according to SS 3064. In this case, the drop weight is 6.0 kg and the tip diameter is 25 mm. The tubes were maintained at -10 ° C or -20 ° C for 24 hours prior to performing a weight loss test. The basis of comparison is a PVC resin prepared by a conventional method in which the stabilizers are dry mixed. The results of the falling weight test are shown in Table 7. The results show that the polymer produced by the process of the present invention is particularly good at breaking strength and that the tubes made therefrom are very useful in cold conditions.

Table 7

Comparative Example 10: Product of Example 11

-10 ° C / 24 h 162 cm 185 cm 212 cm

-20 ° C / 24 h 81 cm 194 cm 209 cm

14-15. example

Polymerization is carried out using the conditions and additives described in Example 2 of U.S. Patent No. 3,862,066. By replacing the paraffin wax and stearamide used as lubricant in the examples of said patent with an olefinic oligomer which is a mixture of a decene tetramer (C 40) and a pentamer (C 50), a corresponding polymer is obtained which is relatively coarse and does not result in waste product. The paraffin wax disclosed in the US patent did not dissolve and disturbed the dispersion. The polymerizations were carried out in an autoclave reactor and the amount of vinyl chloride used was 1,250 kg and the amount of water was 1,850 kg. The additives used for al4 are shown in Table 8, and the resin assay data are shown in Table 8.

Table 8

Additives in g / kg VC

Example 14 Example 15 oligomer - 15 WAX-C 11.8 - IRGAWAX 367 8 - CaCO ₃ 20 20 Ca stearate 11.8 11.8 TiO ₂ 15.9 15.9 epoxidized soybean oil 12 12 NOPCO NXZ (Antifoam Agent) 0.8 0.8

Example 9 resin test Example 15 Example 14 bulk density in kg / m ³ 501 623 porosity (DOP)% 40.3 18.4 particle size D50, μπι 318 289 waste product,% VC 17.8 6.3

• 9 9 ·· · · · · · · · ···· ···

16-19. example

To the polymerization reactor was added 13 kg of vinyl chloride monomer (VCM), 15.6 kg of water and a total dispersion of 1.4 kg of polyvinyl alcohol per kg of VCM. Dicetyl peroxide carbonate was used as an initiator in an amount of 1.3 g / kg VCM. At the beginning of the polymerization, 10 g of lead sulfate is added per kg of VCM. The oligomer used is a hydrogenated decene oligomer containing tetramers (C40), pentamers (C50) and heptamers (C60). The oligomer is added as follows:

Example 16: At the start of the polymerization reaction

Example 17: During the reaction, 40 minutes after the start

Example 18: During the reaction, before depressurization

Example 19: For the suspension after degassing

Table 10

Polymerizations and resin assays

Example Conversion polymerization Volume- particle DOP % time, minutes mass, g / l size, μιη. %

16th 92 261 505 179 21.6 17th 92 272 524 182 20.9 18th 88 301 498 180 19.1 19th 88 303 512 192 21.6

Example 20

The polymerization was carried out according to the procedure of Example 16, except that the oligomer used was prepared from an internal olefin mixture containing 90% C 15 olefin and 10% C 16 olefin. The oligomer contains 47% dimer, 40% trimer and 13% tetramer. The results of the polymerization are as follows:

conversion: 87% polymerization time: 303 minutes bulk density: 516 1 / kg particle size, D50: 17 0 μτη.

plasticizing absorption: 25.3%.

Claims (13)

PATENT CLAIMS A vinyl chloride homo- or copolymer composition which is ready to be processed and contains additives for processing, such as stabilizers, lubricants, colorants, solidifying agents and processing aids, characterized in that vinyl chloride is added to the polymerization reactor at the beginning or during the polymerization. 0.01 to 50% by weight of a chloride olefin oligomer or a mixture of olefin oligomers and an ethylene-olefin copolymer or olefin terpolymer are added. A vinyl chloride homo- or copolymer composition which is ready to be processed and contains additives for processing, such as stabilizers, lubricants, coloring agents, solidifying agents and processing aids, characterized in that it is prepared in the polymerization reactor at the beginning, during or after polymerization. At the end, a liquid olefin oligomer and / or ethylene-olefin copolymer or olefin terpolymer is added in an amount of 0.01 to 50% by weight based on the amount of vinyl chloride. The polymer of claim 1, wherein the vinyl chloride polymer is prepared by slurry polymerization. The polymer of claim 1, wherein the vinyl chloride polymer is prepared by slurry polymerization. Polymer according to claim 1, characterized in that the oligomer is preferably a dimer, a trimer, a tetramer, a pentamer or a hexamer of a C4-C30 alpha-olefin, an inner olefin or a mixture thereof. Polymer according to claim 1, characterized in that the oligomer is preferably a dimer, a trimer, a tetramer, a pentamer or a hexamer of a C4-C30 alpha-olefin, an inner olefin or a mixture thereof. 4. The polymer of claim 1, wherein the oligomer is most preferably an alpha-olefin having from 8 to 14 carbon atoms and having a carbon chain length of from 16 to 100 carbon atoms. 4. The polymer of claim 1, wherein the oligomer is most preferably an oligomer of an α-olefin having from 8 to 14 carbon atoms and having a carbon chain length of from 16 to 100 carbon atoms. 5. The polymer of claim 1, wherein the liquid olefinic polymer is preferably an ethylene-propylene copolymer. 5. The polymer of claim 1, wherein the liquid olefinic polymer is preferably an ethylene-propylene copolymer. - 19 limer. 6. The polymer of claim 1, wherein the liquid olefinic polymer is preferably an ethylene-propylene-diene terpolymer. 6. The polymer of claim 1, wherein the liquid olefinic polymer is preferably an ethylene-propylene-diene terpolymer. 7. The polymer of claim 1, wherein the liquid olefinic polymer is most preferably an ethylene-propylene dicyclopentadiene terpolymer or an ethylene-propylene ethylidene-norbornene. 7. The polymer of claim 1, wherein the liquid olefinic polymer is most preferably an ethylene-propylene dicyclopentadiene terpolymer or an ethylene-propylene ethylidene-norbornene. 8. A process for the preparation of a vinyl chloride homo- or copolymer composition which is ready for processing and comprises processing additives such as stabilizers, lubricants, coloring agents, solidifying agents and processing aids, wherein the vinyl chloride is added to the polymerization reactor at the beginning or during 0.01 to 50% by weight of a chloride olefin oligomer or a mixture of olefin oligomers and an ethylene-olefin copolymer or olefin terpolymer are added. A process for the preparation of a vinyl chloride homo- or copolymer composition which is ready to be processed and contains additives for processing, such as stabilizers, lubricants, colorants, solids and processing aids, characterized in that the polymerization reactor at the beginning of the polymerization or at the end, 0.01 to 50% by weight of a liquid olefin oligomer and / or ethylene olefin copolymer or olefin terpolymer, based on the amount of vinyl chloride. The process according to claim 8, wherein the oligomer is preferably a dimer, trimer, tetramer, pentamer or hexamer of a C 4 -C 30 alpha-olefin, an internal olefin, or a mixture thereof. The process according to claim 8, wherein the oligomer is preferably a dimer, trimer, tetramer, pentamer or hexamer of a C 4 -C 30 alpha-olefin, an internal olefin or a mixture thereof. Process according to claim 8 or 9, characterized in that the oligomer is most preferably an oligomer of an a-olefin having from 8 to 14 carbon atoms having a carbon chain length of from 16 to 100 carbon atoms. Process according to claim 8 or 9, characterized in that the oligomer is most preferably an oligomer of an a-olefin having from 8 to 14 carbon atoms having a carbon chain length of from 16 to 100 carbon atoms. The process according to claim 8, wherein the liquid olefin polymer is preferably an ethylene-propylene copolymer. The process according to claim 8, wherein the liquid olefin polymer is preferably an ethylene-propylene copolymer. The process of claim 8, wherein the liquid olefin polymer is preferably an ethylene-propylene-diene terpolymer. The process of claim 8, wherein the liquid olefin polymer is preferably an ethylene-propylene-diene terpolymer. The process according to claim 8, wherein the liquid olefin polymer is most preferably an ethylene-propylene dicyclopentadiene terpolymer or an ethylene-propylene ethylidene-norbornene. The Trustee · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · ··· · FIXED PATENT CLAIMS 13. The process of claim 8, wherein the liquid olefin polymer is most preferably an ethylene-propylene dicyclopentadiene terpolymer or an ethylene-propylene ethylidene-norbornene.