EP0618938A1 - Method for productional thermostable chemical resistant plastics - Google Patents
Method for productional thermostable chemical resistant plasticsInfo
- Publication number
- EP0618938A1 EP0618938A1 EP92924937A EP92924937A EP0618938A1 EP 0618938 A1 EP0618938 A1 EP 0618938A1 EP 92924937 A EP92924937 A EP 92924937A EP 92924937 A EP92924937 A EP 92924937A EP 0618938 A1 EP0618938 A1 EP 0618938A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- cross
- polymer
- linker
- resistant
- linked
- 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- Withdrawn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
- 238000000034 method Methods 0.000 title claims abstract description 31
- 239000000126 substance Substances 0.000 title claims abstract description 18
- 229920003023 plastic Polymers 0.000 title claims abstract description 17
- 239000004033 plastic Substances 0.000 title claims abstract description 17
- 229920000642 polymer Polymers 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 239000000178 monomer Substances 0.000 claims abstract description 9
- 239000004014 plasticizer Substances 0.000 claims abstract description 9
- 229920001577 copolymer Polymers 0.000 claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- 230000008569 process Effects 0.000 claims abstract description 7
- 239000003381 stabilizer Substances 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims abstract description 5
- 239000000314 lubricant Substances 0.000 claims abstract description 4
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 3
- 239000004971 Cross linker Substances 0.000 claims description 32
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 12
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 claims description 8
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 8
- -1 butyl glycidyl Chemical group 0.000 claims description 8
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 6
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 5
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 4
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims description 3
- 150000008065 acid anhydrides Chemical class 0.000 claims description 3
- 239000001361 adipic acid Substances 0.000 claims description 3
- 235000011037 adipic acid Nutrition 0.000 claims description 3
- 150000001408 amides Chemical class 0.000 claims description 3
- 150000001735 carboxylic acids Chemical class 0.000 claims description 3
- 238000007334 copolymerization reaction Methods 0.000 claims description 3
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 claims description 3
- 229940014800 succinic anhydride Drugs 0.000 claims description 3
- 239000004593 Epoxy Substances 0.000 claims description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 239000012948 isocyanate Substances 0.000 claims description 2
- 150000002513 isocyanates Chemical class 0.000 claims description 2
- 150000004756 silanes Chemical class 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims 1
- 238000003672 processing method Methods 0.000 claims 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 abstract description 2
- 239000003431 cross linking reagent Substances 0.000 abstract 1
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- 150000002367 halogens Chemical class 0.000 abstract 1
- 239000002985 plastic film Substances 0.000 abstract 1
- 229920006255 plastic film Polymers 0.000 abstract 1
- 239000004800 polyvinyl chloride Substances 0.000 description 33
- 229920000915 polyvinyl chloride Polymers 0.000 description 32
- 238000004132 cross linking Methods 0.000 description 24
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 20
- 239000011888 foil Substances 0.000 description 20
- 238000012360 testing method Methods 0.000 description 18
- 239000000203 mixture Substances 0.000 description 17
- 238000003860 storage Methods 0.000 description 11
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 10
- 229920001519 homopolymer Polymers 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000000654 additive Substances 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- WZRRRFSJFQTGGB-UHFFFAOYSA-N 1,3,5-triazinane-2,4,6-trithione Chemical compound S=C1NC(=S)NC(=S)N1 WZRRRFSJFQTGGB-UHFFFAOYSA-N 0.000 description 3
- IXDGHAZCSMVIFX-UHFFFAOYSA-N 6-(dibutylamino)-1h-1,3,5-triazine-2,4-dithione Chemical compound CCCCN(CCCC)C1=NC(=S)NC(=S)N1 IXDGHAZCSMVIFX-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 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
- 125000001309 chloro group Chemical group Cl* 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000035882 stress Effects 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 125000000746 allylic group Chemical group 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 2
- 239000012038 nucleophile Substances 0.000 description 2
- 235000019198 oils Nutrition 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 235000012424 soybean oil Nutrition 0.000 description 2
- 150000003918 triazines Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 102100035474 DNA polymerase kappa Human genes 0.000 description 1
- 101710108091 DNA polymerase kappa Proteins 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 206010073306 Exposure to radiation Diseases 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000008642 heat stress Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- MYWUZJCMWCOHBA-VIFPVBQESA-N methamphetamine Chemical compound CN[C@@H](C)CC1=CC=CC=C1 MYWUZJCMWCOHBA-VIFPVBQESA-N 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229920013730 reactive polymer Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 230000001960 triggered effect Effects 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
-
- 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/34—Introducing sulfur atoms or sulfur-containing groups
-
- 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/46—Reaction with unsaturated dicarboxylic acids or anhydrides thereof, e.g. maleinisation
-
- 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
- C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
- C08F2800/20—Copolymer characterised by the proportions of the comonomers expressed as weight or mass percentages
-
- 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
- C08F2810/00—Chemical modification of a polymer
- C08F2810/20—Chemical modification of a polymer leading to a crosslinking, either explicitly or inherently
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2327/00—Characterised by the use of homopolymers or 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; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or 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; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/04—Characterised by the use of homopolymers or 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; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08J2327/06—Homopolymers or copolymers of vinyl chloride
Definitions
- the invention concerns a procedure for the production of thermostable chemical-resistant plastic. Extremely high resistance to chemicals can be achieved if a strong, homogenous cross-linked network is introduced into the polymer.
- This type of polymer will be particularly suitable for applications where oil- resistance is important, for example in oil booms. It is also suitable for foils, tarpaulins, membranes and as a hard-wearing top layer for floor coverings. Cables, pipes and rainwear can also be mentioned as potential application areas.
- cross-linking has long been considered a good method of improving the mechanical properties of this plastic at high temperatures. Many attempts have therefore been made to find technical solutions to this problem.
- reactive plasticizers such as difunctional and trifunctional acrylates or methacrylates.
- thermostability of the product because of the degrading effect of the radiation or the free radicals (see for example W. A. Salmon & L. D. Loan; J. Appl. Polym. Sci., 16, 671, (1972)).
- a homopolymer of polyvinyl chloride has a certain content of reactive groups, inasmuch as the carbon-chlorine bond is polar and may be attacked by nucleophilic compounds.
- thiolate ions have proved to be good nucleophiles (see for example. K. Mori & Y. Nakamura; J. Macromol. Sci. Chem. A12, (2), 209, (1978)).
- Mori and Nakamura have described cross-linking of PVC with various types of dithiol triazines.
- the object of the invention is therefore to produce a thermostable chemical-resistant halogenous plastic, specifically a polyvinyl chloride.
- a thermostable chemical-resistant halogenous plastic specifically a polyvinyl chloride.
- PVC polyvinyl chloride
- the cross-linking reaction can be carried out concurrently with the working of the material without requiring very much extra heat.
- the present invention concerns a procedure for producing a chemical-resistant halogenous plastic. Reactive groups are added to a halogenous polymer and cross-linked by reaction with a multifunctional organic compound under the influence of heat during or after the processing.
- PVC is a preferred polymer, but the method is applicable to the production of cross-linked products from other halogenous polymers too.
- the invention also concerns a chemical-resistant cross-linked plastic which consists of 20-98% of copolymer of vinyl chloride and a glycidylic monomer, 0-80% of plasticizer, 0.05-10% of a multifunctional organic cross-linker, 0.1-10% of stabilizer and 0-3% of lubricant.
- This plastic in oil and chemical-resistant products, especially foils, is also covered by the invention.
- PVC is one of the great thermoplastics and is regarded as a "mature" product. All the same, there is a steady increase in the consumption of PVC, and new areas of application are still being developed.
- PVC is mainly produced by means of suspension, emulsion, microsuspension or mass polymerization. The bulk of the PVC produced is homopolymeric.
- the unique feature of PVC is that it can be mixed with a great number of organic solvents, and this means that products at all grades of plasticity can be manufactured.
- defect structures which arise in the polymer chain during polymerization. These defect structures can be allylic and tertiary chlorine groups as illustrated below.
- a halogenous polymer which has had extra reactive groups added, which in reaction with suitable cross-linkers can produce a strong, homogenous network. It is an advantage if the extra reactive groups are already added during polymerization. The polymer can then in itself be regarded as reactive.
- comonomers of vinyl chloride there are a number of relevant comonomers of vinyl chloride in this respect, and the choice of reactive group in the monomer can be made from, for example, epoxy (glycidyl), carboxylic acids, acid anhydrides, hydroxyl, amines, amides, isocyanates and silanes.
- Glycidylic acrylates or methacrylates have provedd particularly favourable. This is because they are easily copolymerized with vinyl chloride in emulsion or suspension polymerization, and they are quickly used up so that there is no enrichment of them in the monomer phase.
- the epo xy groups have a suitable reactivity in the conditions in which the cross-linking has to be done.
- Copolymerization of vinyl chloride and a glycidylic acrylate or methacrylate is as mentioned above an example of the way epoxy groups can be introduced into a halogenous polymer.
- GA glycidylic acrylate or methacrylate
- the comonomer can be added in a freely-selected way, but it is an advantage if an even distribution of reactive groups in the polymer can be achieved.
- the polymer can also be produced as a standard PVC with the above-mentioned techniques.
- Glycidyl acrylate and butyl glycidyl acrylate are also suitable monomers.
- the cross-linker can be any multifunctional compound which is coreactive with the polymer's reactive groups - for example acid anhydrides, carboxylic acids, amines, amides, mercaptans, thiol triazines, amidazoles.
- Special preferences are phthalic anhydride, maleic anhydride, succinic anhydride, succinic acid, malonic acid, oxalic acid, adipic acid, 2- dibutylamino-4,6-dithiol triazine, 2,4,6-trithiol triazine and 1,6-hexane diamine.
- catalysts e.g. of the tertiary amine or Lewis acid types
- the cross-linker may also be another reactive polymer containing the above-mentioned groups.
- the type of cross-linker which will give the desired result will depend on the total reaction system and reaction conditions.
- the cross-linker may be added at an arbitrarily chosen point in time, also before the actual polymerizate dries.
- cross-linking take place when the copolymer produced is mixed with the cross-linker, and there is a direct reaction between these while the product is being processed. If the cross-linker is a difunctional amine the reactions can be illustrated follows :
- Foils of varying composition are produced from both paste PVC and S-PVC. Different types of cross-linkers were used. The production method for the foils and methods of testing them are described below. If not otherwise stated, quantities are given in pph (weight parts per hundred parts of polymer).
- the paste is mixed in a Hobart mixer in accordance with the ingredients given in Tables 1-3.
- the paste is stroked on to release paper immediately after mixing and gelatinized/rolled and if necessary pressed as described in Tables 1-3.
- the mixing is done in a small Papenmeier mixer. All solids are mixed together from the start at “low” agitation.
- the plasticizer (DOP) is added when the temperature has reached 65°C.
- the mixing then continues at "high” speed until the temperature reaches 110°C.
- the powder is then cooled down to 40°C.
- the degree of cross-linking in the foils is also assessed by stress relaxation tests in a dynamic spectrometer (Rheometrics RDS 7700). The conditions are given in Tables 1-2. The values given as percentages are the ratio between the stress relaxation module initially and after 100 seconds measured at 8% constant deformation.
- the foils are stored in diesel for seven full days. Before and after storage in diesel the foils are analysed for tensile strength, elongation before breakage, cold-flex temperature and weight changes.
- Weight change after storage in diesel was calculated on the basis of the weight of the foil before and after storage. Before the foil was weighed after storage, it was dried with absorbent paper and only weighed 24 hours later.
- Lankromark LZ616 Ca/Zn stabilizer from Lankro.
- Zisnet DB 2-dibutylamino-4, 6-dithiol triazine from Sankyo asei.
- the gelatinizing temperature has a positive effect on the result, as gelatinization at 190°C produces better cross-linking than treatment at 170°C. A longer gelatinizing time also affects the result, as can be seen by comparing the mixtures B-6 and B-7.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NO915081 | 1991-12-23 | ||
| NO915081A NO175596C (no) | 1991-12-23 | 1991-12-23 | Kjemikalieresistent kryssbundet plast samt fremstilling og anvendelse av denne |
| PCT/NO1992/000194 WO1993013161A1 (en) | 1991-12-23 | 1992-12-09 | Method for productional thermostable chemical resistant plastics |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP0618938A1 true EP0618938A1 (en) | 1994-10-12 |
Family
ID=19894709
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP92924937A Withdrawn EP0618938A1 (en) | 1991-12-23 | 1992-12-09 | Method for productional thermostable chemical resistant plastics |
Country Status (11)
| Country | Link |
|---|---|
| EP (1) | EP0618938A1 (en, 2012) |
| JP (1) | JPH07502555A (en, 2012) |
| CN (1) | CN1076204A (en, 2012) |
| AU (1) | AU3097492A (en, 2012) |
| CA (1) | CA2126576A1 (en, 2012) |
| FI (1) | FI943023L (en, 2012) |
| HU (1) | HUT68290A (en, 2012) |
| NO (1) | NO175596C (en, 2012) |
| RU (1) | RU94031163A (en, 2012) |
| TW (1) | TW222658B (en, 2012) |
| WO (1) | WO1993013161A1 (en, 2012) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2741083B1 (fr) * | 1995-11-13 | 1999-02-19 | Nobel Plastiques | Procede d'ignifugation d'un composant en matiere plastique appartenant a une installation de distribution d'un liquide inflammable |
| WO1996023656A1 (fr) * | 1995-02-02 | 1996-08-08 | Nobel Plastiques | Procede d'ignifugation d'un composant en matiere plastique appartenant a une installation de distribution d'un liquide inflammable |
| CN106188707A (zh) * | 2015-05-04 | 2016-12-07 | 电气化学工业株式会社 | 氯丁二烯橡胶组合物、硫化成型体及其用途 |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4871801A (en) * | 1988-11-25 | 1989-10-03 | The B. F. Goodrich Company | Reactive polyvinyl chloride and polymer products made therefrom |
| NO166189C (no) * | 1989-02-08 | 1991-06-12 | Norsk Hydro As | Tverrbundet termostabil polymer og fremstilling derav. |
-
1991
- 1991-12-23 NO NO915081A patent/NO175596C/no unknown
-
1992
- 1992-12-09 RU RU94031163/04A patent/RU94031163A/ru unknown
- 1992-12-09 WO PCT/NO1992/000194 patent/WO1993013161A1/en not_active Application Discontinuation
- 1992-12-09 EP EP92924937A patent/EP0618938A1/en not_active Withdrawn
- 1992-12-09 JP JP5511571A patent/JPH07502555A/ja active Pending
- 1992-12-09 CA CA002126576A patent/CA2126576A1/en not_active Abandoned
- 1992-12-09 AU AU30974/92A patent/AU3097492A/en not_active Abandoned
- 1992-12-09 HU HU9401894A patent/HUT68290A/hu unknown
- 1992-12-09 FI FI943023A patent/FI943023L/fi unknown
- 1992-12-23 CN CN92115363.5A patent/CN1076204A/zh active Pending
-
1993
- 1993-01-14 TW TW082100193A patent/TW222658B/zh active
Non-Patent Citations (1)
| Title |
|---|
| See references of WO9313161A1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| NO175596B (no) | 1994-07-25 |
| FI943023A7 (fi) | 1994-07-27 |
| CN1076204A (zh) | 1993-09-15 |
| TW222658B (en, 2012) | 1994-04-21 |
| CA2126576A1 (en) | 1993-07-08 |
| FI943023L (fi) | 1994-07-27 |
| FI943023A0 (fi) | 1994-06-22 |
| WO1993013161A1 (en) | 1993-07-08 |
| HUT68290A (en) | 1995-06-28 |
| RU94031163A (ru) | 1996-05-27 |
| JPH07502555A (ja) | 1995-03-16 |
| NO175596C (no) | 1994-11-02 |
| NO915081D0 (no) | 1991-12-23 |
| HU9401894D0 (en) | 1994-09-28 |
| AU3097492A (en) | 1993-07-28 |
| NO915081L (no) | 1993-06-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US3804925A (en) | Acrylic resinous composition and process therefor from a 3-stage emulsion polymerization system | |
| EP0456746B1 (en) | Crosslinked halogen-containing polymer | |
| EP0171850B2 (en) | Use of polyaminoamide resins as adhesion promoters of PVC plastisols | |
| JPS6071666A (ja) | 改善された衝撃強度を有する合成樹脂組成物 | |
| US5561191A (en) | Method for the production of silane containing crosslinked PVC copolymer | |
| EP0618938A1 (en) | Method for productional thermostable chemical resistant plastics | |
| US3341628A (en) | Blends of isotactic polyvinyl chloride and postchlorinated atactic polyvinyl chloride | |
| US2789959A (en) | Perfluorochloroolefin homopolymer plasticized with perchloroolefin copolymers | |
| CS220792B2 (en) | Self-extinguishing impact resistant mixture | |
| DE2127840B2 (de) | Härtbare Formpulver | |
| DE69303850T2 (de) | Fluor enthaltende Überzugszusammensetzung | |
| US3723570A (en) | Ethylene-vinyl acetate-allyl glycidyl ether terpolymer with polyvinyl chloride | |
| JP3361094B2 (ja) | 自由流動性の粉末ポリ塩化ビニル組成物 | |
| US2673191A (en) | Light stable vinylidene chloride polymer compositions | |
| JP2570827B2 (ja) | 水性分散液の製造方法および水性塗料組成物 | |
| US4520169A (en) | Elastomeric sol/gel blends | |
| US4778841A (en) | Plastic materials for the production of deep-drawn films | |
| US3291862A (en) | Chlorinated polyolefin polymer mixtures | |
| JPH02191606A (ja) | 反応性ポリ塩化ビニルおよびこれから製造したポリマー製品 | |
| SU1002324A1 (ru) | Наполненна композици на основе поливинилхлорида | |
| US5189087A (en) | Plastic materials for the production of deep-drawn films | |
| Sundbø et al. | Preparation of crosslinked and thermostable paste poly (vinyl chloride) | |
| SU994518A1 (ru) | Композици дл получени покрыти искусственной кожи | |
| KR910007594B1 (ko) | 염화비닐계 수지조성물 | |
| JP2631036B2 (ja) | 架橋ポリマー用組成物およびその製造方法 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
| 17P | Request for examination filed |
Effective date: 19940618 |
|
| AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE CH DE DK ES FR GB GR IT LI LU MC NL PT SE |
|
| 17Q | First examination report despatched |
Effective date: 19951113 |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION HAS BEEN WITHDRAWN |
|
| 18W | Application withdrawn |
Withdrawal date: 19960830 |