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
  • C08F8/00—Chemical modification by after-treatment
  • C08F8/42—Introducing metal atoms or metal-containing groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L27/00—Compositions 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; Compositions of derivatives of such polymers
  • C08L27/02—Compositions 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; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L27/04—Compositions 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; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/15—Heterocyclic compounds having oxygen in the ring
  • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
  • C08K5/1515—Three-membered rings

Definitions

• the present invention concerns white or light-coloured thermostable cross-linked halogen containing polymers and a procedure for producing them.
• organosilanes are used as cross-linkers.
• the patent application DE 3719151 describes the use of organosilanes, especially mercaptosilanes (e.g. mercaptopropyl trimethoxysilane (I)) as cross-linking agents for halogen containing polymers, especially the homopolyroer PVC.
• the cross-linking is done as follows:
• First trimethoxysilane (I) is grafted on to the polymer chain, and this should preferably be done by a normal process such as compounding, extrusion or rolling.
• the cross-linking reaction is then carried out in two steps: By hot water or steam treatment alkoxysilanes are hydrolysed and form silanols. Once the silanols have been formed they quickly react with one another and form the cross link through condensation of H 2 O:
• halogen containing polymers consist of copolymers of halogen containing monomer and glycidyl acrylates.
• the preferred copolymers are copolymers between vinyl chloride monomer (VCM) and glycidyl methacrylate (GMA).
• VCM vinyl chloride monomer
• GMA glycidyl methacrylate
• the Norwegian patent application first and foremost differs from DE 3719151 in that the epoxy group introduced by the glycidyl monomers facilitates the grafting of the organosilanes to the polymer chain.
• the dominant grafting reaction is assumed to take place as follows, where a copolymer of VCM and 0.05-10% of glycidyl methacrylate are used together with (I):
• the colouring limits the usefulness of this cross-linking technique, since even after the addition of large quantities of the white pigment titanium oxide there is still a yellowish tone. This means that the cross-linking method cannot be used when whiteness is an important requirement.
• the colour is moreover unstable, showing a tendency to change under the influence of sunlight, for example. It is also difficult to add other colours, especially light colours.
• the object of the invention is thus to avoid the disadvantages of the methods described above and to obtain a cross-linked halogen containing polymer with a white or light colour.
• a further objective is to strengthen the network.
• the present invention concerns a method of producing white or light-coloured thermostable cross-linked halogen containing polymer. Surprisingly, it was found that this polymer can be produced using mercaptosilane, lead stabilizer and a low- molecular epoxy compound. The low-molecular epoxy compound reacts with the mercaptosilane and/or the by-products which together with the lead stabilizer cause the colouring, and thus remedies the problem.
• the polymer consists of 30-98 weight % halogen containing polymer, 0-60 weight % plasticizer, 0.05-10 weight % hydrolysable mercaptosilane, 0.1-10 weight % lead stabilizer, 0-4 weight % lubricant and 0.1-10 weight % epoxy resin.
• the halogen containing polymer may be a homopolymer like PVC, or a copolymer based on halogen containing polymer and inactive or reactive comonomers with respect to the cross-linking.
• a copolymer between a halogen containing monomer and a glycidyl- containing acrylate is favoured.
• the content of glycidyl- containing acrylate is 0.05-10 weight %. Under 0.05 weight % the effect is too weak and over 10% the polymerization is too slow.
• the mercaptosilane is of the general formula:
• R' a -CH 2 - -C 2 H 4 - up to C 8 H 16 or another non-functional group.
• R'' a freely selected, non-hydrolysable group
• Y one or more hydrolysable groups such as -OCH 3 , -OC 2 H 5 ,
• the compound R" can be a freely selected non-hydrolysable group.
• Examples of usable groups are -CH 2 - up to C 8 H 17 , but the choice of groups in principle has no significance for the result.
• the lead stabilizer is a freely selected commercial stabilizer based on e.g. tribasic lead sulphate, tetrabasic lead sulphate, dibasic lead phosphite, dibasic lead carbonate, dibasic lead phthalate.or dibasic lead stearate.
• the upper limit is fixed according to whatever is practical, there is no level that cannot be exceeded.
• the disadvantages of high additions are more expense and higher density.
• a practical limit is 10 weight %.
• the low-molecular epoxy compound may consist of e.g. monofunc- tional or multifunctional glycidyl ethers, glycidyl esters, glycidyl amines, or of a linear or cycloaliphatic type. This is added at 0.1-10 weight %. An addition of less than 0.1% has no effect and an addition over 10% produces too great a surplus of epoxy resin in proportion to the mercaptosilane. In addition the mixture may contain small quantities of the ordinary additives used for this type of product.
• DGEBA resin commercial epoxy resin of diglycidyl ether-bisphenol A type, known as DGEBA resin.
• Hot-set Measured as the deformation caused by a load of 0.1 MPa on a sample rod at 200° C after 15 mins., and as the residual deformation 5 mins. after the load has been removed from the sample.
• Example 3 shows that it is possible to produce white material which is strongly cross-linked by adding a low-molecular epoxy compound to the already familiar reaction between mercaptosilane, epoxy-containing halogen containing comonomer and lead stabilizer.
• the fact that the gel content decreases through addition of epoxy resin and that the deformation by heat also becomes greater is very probably a function of the fact that the low-molecular epoxy compound "steals" mercaptosilane from the epoxy- groups bonded in the chain.
• hydrolysed and condensed compounds of type (IV) have a positive effect on the hot-set, but it is no less effective than if (I) were grafted to the polymer chains.
• Example 4 shows that an increase of the amount of epoxy in the polymer chains can produce a white material with lower low- molecular epoxy resin content.
• the example shows the same tendency as Example 3, inasmuch as addition of epoxy resin decreases the gel content and increases the hot-set deformation.
• Cycloaliphatic epoxy resins are considered less reactive with mercaptan groups than for example diglycidyl ether-based epoxy resins like those of the DGEBA type.
• the higher gel content and the lower deformation than when DGEBA resin is used may be due to the fact that the cycloaliphatic epoxy resin does not compete as well with the polymer-based epoxy groups for (I).
• Example 3-5 the addition of low-molecular epoxy resin has produced a lighter or white material at the expense of a rather poorer cross-linking.
• the epoxy resin in all these experiments has been difunctional, and the mercaptosilane has been tetra- functional. This has clearly not been sufficient to make an overall positive contribution to the mechanical durability of the network in terms of hot-set values.
• Example 6 the addition of low-molecular epoxy resin has produced a lighter or white material at the expense of a rather poorer cross-linking.
• the epoxy resin in all these experiments has been difunctional, and the mercaptosilane has been tetra- functional. This has clearly not been sufficient to make an overall positive contribution to the mechanical durability of the network in terms of hot-set values.
• Example 6 Example 6 :
• Example 6 shows that the use of a tetrafunctional resin makes a contribution to the mechanical durability of the network, at least with additions of small quantities.
• the fact that the material turns light yellow is presumably due to the fact that Araldit 0163 itself is an intense yellow colour.
• the lower gel content than in Example 3 can be explained by the fact that the epoxy content is higher per weight unit in the tetrafunctional resin than in the DGEBA resin.

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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)
• Epoxy Resins (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Paints Or Removers (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Applications Claiming Priority (3)

Publications (1)

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ID=19894424

Family Applications (1)

Country Status (13)

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Family Cites Families (4)

• 1991
  • 1991-09-03 NO NO913441A patent/NO173337C/no unknown
• 1992
  • 1992-08-17 AU AU24749/92A patent/AU666494B2/en not_active Ceased
  • 1992-08-17 EP EP92918039A patent/EP0605446A1/en not_active Withdrawn
  • 1992-08-17 KR KR1019940700698A patent/KR940702205A/ko active IP Right Grant
  • 1992-08-17 WO PCT/NO1992/000131 patent/WO1993005112A1/en not_active Application Discontinuation
  • 1992-08-17 JP JP5505119A patent/JP2631036B2/ja not_active Expired - Lifetime
  • 1992-08-17 CA CA002116861A patent/CA2116861A1/en not_active Abandoned
  • 1992-08-17 HU HU9400643A patent/HUT68670A/hu unknown
  • 1992-08-17 BR BR9206453A patent/BR9206453A/pt not_active Application Discontinuation
  • 1992-09-03 CN CN92110104A patent/CN1036401C/zh not_active Expired - Fee Related
  • 1992-09-03 PT PT100835A patent/PT100835A/pt not_active Application Discontinuation
  • 1992-09-04 TW TW081107013A patent/TW254959B/zh active
• 1994
  • 1994-03-02 FI FI940996A patent/FI940996A/fi not_active Application Discontinuation

Non-Patent Citations (1)

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