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.

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• 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)
• Compositions Of Macromolecular Compounds (AREA)

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• 1991
  • 1991-12-23 NO NO915081A patent/NO175596C/no unknown
• 1992
  • 1992-12-09 WO PCT/NO1992/000194 patent/WO1993013161A1/en not_active Application Discontinuation
  • 1992-12-09 RU RU94031163/04A patent/RU94031163A/ru unknown
  • 1992-12-09 EP EP92924937A patent/EP0618938A1/de 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 HU HU9401894A patent/HUT68290A/hu unknown
  • 1992-12-09 AU AU30974/92A patent/AU3097492A/en not_active Abandoned
  • 1992-12-23 CN CN 92115363 patent/CN1076204A/zh active Pending
• 1993
  • 1993-01-14 TW TW82100193A patent/TW222658B/zh active
• 1994
  • 1994-06-22 FI FI943023A patent/FI943023A/fi unknown

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