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WO1986002036A1 - Produit a base de mousse de chlorure de polyamide et procede de production - Google Patents

Produit a base de mousse de chlorure de polyamide et procede de production Download PDF

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Publication number
WO1986002036A1
WO1986002036A1 PCT/NO1985/000053 NO8500053W WO8602036A1 WO 1986002036 A1 WO1986002036 A1 WO 1986002036A1 NO 8500053 W NO8500053 W NO 8500053W WO 8602036 A1 WO8602036 A1 WO 8602036A1
Authority
WO
WIPO (PCT)
Prior art keywords
product
pressure
blowing agent
pvc
polyvinyl chloride
Prior art date
Application number
PCT/NO1985/000053
Other languages
English (en)
Inventor
Baard Spydevold
Original Assignee
Master Marine A.S
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Master Marine A.S filed Critical Master Marine A.S
Publication of WO1986002036A1 publication Critical patent/WO1986002036A1/fr

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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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
    • 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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
    • C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
    • 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
    • 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
    • C08J2427/00—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
    • 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
    • C08J2433/00—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 only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers

Definitions

  • the present invention relates to a product for producing a polyvinyl chloride foam and the process for producing same.
  • Polyvinyl chloride foam also called PVC foam
  • Nitrogen can, for example, be mixed into the polymer melt under high pressure (approx. 200 bar) according to the Airex method.
  • a dissolution or dispersion of the blowing agent will in this way be brought about in the melted polymer when the blowing agent and the polymer for exaroole are mixed in an extruder.
  • the decomposed blowing agent in the polymer melt will expand and cause the polymer to rise (swell up).
  • the expanded product is also cooled to a temperature lower than the polymer's second order transition temperature, Tg, causing the foam to become self-supporting.
  • a problem in the production of polyvinyl chloride' foam has consisted in keeping it in the form of an intermediate product, where the blowing agent has been decomposed and the polyvinyl chloride is present in an unexpanded, but gelled state.
  • Such an intermediate product will be highly suitable when expansion is wanted at a later point of time and when con ⁇ ditions on site indicate that it is advantageous to use an intermediate product which has already been prepared for expansion. It is for example possible to picture this inter ⁇ mediate product being used to fill an enclosed cavity in buoyancy elements, in that a measured amount of the pre ⁇ fabricated intermediate product is introduced into the cavity and then subjected to the effects- of heat so that it expands and completely fills the cavity.
  • the aim of the present invention is therefore to produce an intermediate product and to produce it in such a way that the resulting foam product is produced by a method which is far more simple and reasonable than the press process described above.
  • the present invention relates to an intermediate product based on a PVC foam mix and the process of producing this product, in which the polyvinyl chloride resin is mixed with the blowing agent, stabilizer and any other possible process-regulation additives, producing a carefully worked and what is called a gelled mixture which, in the form of a shaped, solid material, is transferred to a high-pressure heating device for decomposing the blowing agent in the mix ⁇ ture without the mixture to expand, after which the mixture with the decomposed blowing agent is cooled under pressure. Once the pressure has been released, it will -later be possible to expand the intermediate product obtained into polyvinyl chloride foam.
  • the process is characterized in that the mixture of polyvinyl chloride, stabilizer, blowing agent and any other possible process-regulation additives, is transferred to an extruder or other suitable plastic processing machine, in which the mixture is kneaded without the blowing agent being decomposed and, if the machine is an extruder, extruded in any shape whatsoever, its length and breadth depending on the design of the extrusion nozzle, and made to solidify, after which the extruded, solidified mix ⁇ ture is transferred to an autoclave in which a pressure-exchanging and barrier-forming medium is circulating at a pressure of 20-300 bar and at a temperature of 50-270°C, and heat-treated in the autoclave for a period of 5-80 minutes in order to decompose the blowing agent in the extruded and solidified product, after which the hot medium which is circulating is replaced by a colder medium of the same type in order to reduce the temperature in the autoclave to below the second order transition temperature, Tg, of the pressure-
  • the polymer mass can be mixed and gelled in an extruder. This is however only one of the types of plastic processing machines which can be used with regard to the production of the PVC foam mixture.
  • Injection moulding machines and kneading machines are also suitable for the said purpose.
  • kneading machines parti ⁇ cularly Banbury mixers can be mentioned as being suitable for mixing and pregelling the said PVC foam, but other types of Sigma mixers can also be used.
  • the invention therefore does not lay down any conditions regarding the type of plastic processing machine to be used, except that it should be suited for the purpose, i.e. that it can mix the components into a PVC foam mixture and pregel it.
  • both solid and liquid blowing agents can be used in the PVC foam mixture.
  • the invention is especially characterized in that, unlike conventional methods, the decomposition of the blowing agent in the extruded product does not take place in an expensive high-pressure press with its great need for sealing in order to prevent gas escaping from the decomposed blowing agent during treatment in the high-pressure press, but in an auto ⁇ clave or high-pressure chamber in which both the pressure and the temperature are " produced by a circulating medium.
  • this medium is replaced by the same medium in a colder state.
  • the pressure- and heat-treated extruded mixture is then cooled to below the temperature at which the gas from the blowing agent would have been able to expand the polyvinyl chloride after the pressure release of the autoclave.
  • the polyvinyl chloride used can be a homopolymer PVC and/or a copolymer an /or a postchlorinated PVC of the S-PVC and/or E-PVC type.
  • the mixture contains a polyacrylate, preferably in a quantity of approx. 6-30 parts per 100 parts of polyvinyl chloride.
  • blowing agent azodicarbonamide has turned out to be very suitable although other gas-generating blowing agent, which are decomposed in the temperature range of 130-250 C and at a pressure of 50-300 bar, also can be used.
  • Some zinc oxide as a "kicker" together with some lubri ⁇ cant in the form of a mixture of polyethylene wax, paraffin wax or calcium-stearate is particularly advantageous.
  • the mixture may also contain a certain amount of softener and also a certain amount of isocyanate to increase the heat resistance of the foam.
  • a particular requirement of the invention is that the decom ⁇ position of the blowing agent is carried out under high pressure and at high temperatures using a medium which should have low solubility for the gases generated by the blowing agent.
  • ther ⁇ o-regulating medium used has a barrier-forming effect, in that the gases formed from the blowing agent are either insoluble or soluble to a particularly small extent in the medium.
  • medium in this connection is meant the use of for example glycerol or brine with a certain salt content.
  • blowing agent gives off nitrogen (N 2 ) and carbon monoxide (CO), as is the case with azodicarbonamide, but other liquids, which have the advantageous properties stated above, can also be used, for example synthetic oils (Shell N-8401).
  • glycerol could advantageously be used as a pressure- and heat-exchanging medium in the autoclave, as glycerol has a high boiling point and is particularly resistant to decom ⁇ position at high temperatures and possesses, moreover, low solubility for nitrogen (N 2 ) which is one of the products generated during the decomposition of the azodicarbonamide.
  • the autoclave itself may have any length and section since possible limitations only will be due to design and space consideration.
  • the homogeneously mixed, pregelled product which for example comes from the extruder during the execution of the present method, can thus be extruded in the form of a continuous length with a breadth and thickness suitable for autoclaving in an autoclave.
  • the continuous length can also be divided into bits before the autoclaving.
  • the pressure- and heat-treated intermediate product can be divided into pieces of any size for subsequent expansion in already known way at any place where this might be desired.
  • the expansion itself is carried out by subjecting the pressure- and heat-treated pieces, which contain the decom ⁇ posed blowing agent, to increased temperature. In this way, the pressure of the gas in these pieces increases, so that the pieces by the temperature used will swell up, thereby achieving an expanded state.
  • An advantageous way of carrying out expansions in a limited cavity is by introducing super ⁇ heated water vapour at approx. 105 C.
  • the intermediate product containing the decomposed blowing agent will thereby expand as a result of the internally increased gas pressure and the reduced deformation resistance of the polyvinyl chloride, and with suitable control of the expansion process, it is easy to obtain polyvinyl chloride foam , with a relative density of for example 0.08 to 0.5 kg/1.
  • the polyvinyl chloride foam has a structure with relatively small, non-interconnected pores. It is relatively hard and has a substantial deformation resistance after being deformed (compression set), for example as a result of compression. It has above all, due to its special pore structure and the polymer's hydrophobia, a very low absorption level with regard to water. Its level of heat insulation is also very good, and because of its relative low density and low absorption level with regard to water, it is particularly suitable as buoyancy material for objects which are to be used in contact with water.
  • mooring buoys As an example of such objects -can be mentioned mooring buoys, seamarks, net floats and hollow offshore structures where the buoyancy must be ensured and where at the same time any possible damage to the structure surrounding the polyvinyl chloride should entail as little absorption of water by the buoyancy material as possible. For this reason the product manufactured by the present method is particularly suitable for use as insulation and buoyancy material in platform legs for use in offshore structures.
  • the powder mixture is added to a single-screw extruder or an injection moulding machine, where the PVC mass is heated to approx. 160 C.
  • the kneaded and pregelled mass is then extruded in a strip which is cooled.
  • the strip can be wound up into a roll, cut into suitable lengths or granulated and used' in such a form for the subse ⁇ quent autoclaving.
  • 25 kg pregelled PVC granulate and 20 litres of glycerol or synthetic oil (Shell N-8401) are added to a 50 litre auto ⁇ clave, after which the autoclave is closed and the air there ⁇ in replaced with nitrogen.
  • the glycerol or oil is then heated to 180°C in a separate heating vessel outside the autoclave and circulates, to and from the autoclave through this.
  • the blowing agent in the pregelled product will be decomposed as soon as the decomposition temperature is reached. This will be within the temperature range of 155-200 C, depending on the amount of "kicker". Without “kicker", decom ⁇ position can only be expected at temperatures above 235 C.
  • the hot glycerol or oil is forced out of the autoclave and into a tank while, at the same time, cold glycerol or oil is added and the pressure in the autoclave and appurtenant connecting equipment is maintained.
  • Tg second order transition temperature
  • the glycerol or oil is drawn off and the PVC mass poured into a centrifuge for separation of the additional glycerol. Thereafter the PVC mass is washed with clean water in the same device.
  • Example 2 The PVC foam is then dried ' and packed in bags for later use in situ.
  • Example 2 The PVC foam is then dried ' and packed in bags for later use in situ.
  • Example 1 Instead of the mixture according to Example 1, the tin stabilizer is replaced with Ba and Pb stabilizer with 2.0 parts of each and 2.0 parts of toluene di-isocyanate. The zinc oxide is removed from the formulation. Then the raw materials are mixed and the decomposed, unexpanded PVC foam will be produced according to Example 1.
  • suitable moulded objects are injection moulded, which are either autoclaved as they are or granulated.
  • the decomposed, unexpanded PVC foam mass is then produced according to Example 1.
  • Example 5 The formulation according to Example 1 is added to a Banbury mixer and kneaded and pregelled therein. The decomposed, unexpanded PVC foam mass is then produced according to Example 1.
  • Example 5 The formulation according to Example 1 is added to a Banbury mixer and kneaded and pregelled therein. The decomposed, unexpanded PVC foam mass is then produced according to Example 1.
  • Example 1 The formulation according to Example 1 is mixed, pregelled, granulated and autoclaved, but instead of glycerol as a heat-exchanging and barrier-forming medium, brine (approx. 30 g common salt per 100 g water) is used.
  • brine approximately 30 g common salt per 100 g water
  • Emulsion PVC 100.0 parts
  • a copolymer emulsion polyvinyl chloride with 97 weight per cent polyvinyl chloride and 3 weight per cent vinyl acetate is used instead of homopolymer polyvinyl chloride.
  • Example 1 When the polyvinyl-chloride intermediate product which results from embodiments 1-8 is used in a measured amount for expansion on site, it will, as a result of the temperature increase during expansion, soften to such an extent that each one of the expanded PVC pieces will fuse together, thereby forming a whole in the cavity to be filled with PVC foam.
  • the intermediate product can on beforehand be surface-treated with a fusing aid, for example hot-melt glue or a glue of an ordinary type (for example water-based emulsion glue).
  • a fusing aid for example hot-melt glue or a glue of an ordinary type (for example water-based emulsion glue).

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

Ce produit, destiné au remplissage in situ de corps creux, est mélangé et prégélifié par un procédé connu dans une machine de traitement de matières plastiques. Pendant cette phase du procédé l'agent gonflant dans le produit n'est pas décomposé. La décomposition de l'agent gonflant n'a lieu que dans un autoclave, par l'utilisation d'un milieu échangeur de température et de pression et formant une barrière. Lorsque la décomposition de l'agent gonflant est achevée, un milieu plus froid est introduit dans l'autoclave pour refroidir le produit à une température inférieure à sa température de transition de deuxième ordre, Tg. Le produit peut être alors converti en un matériau moussant par chauffage in situ à l'endroit d'expansion.
PCT/NO1985/000053 1984-09-27 1985-09-13 Produit a base de mousse de chlorure de polyamide et procede de production WO1986002036A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
NO843876A NO843876L (no) 1984-09-27 1984-09-27 Produkt p¨ basis av skumpolyvinylklorid og fremgangsm¨te f or fremstilling av samme
NO843876 1984-09-27

Publications (1)

Publication Number Publication Date
WO1986002036A1 true WO1986002036A1 (fr) 1986-04-10

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ID=19887863

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PCT/NO1985/000053 WO1986002036A1 (fr) 1984-09-27 1985-09-13 Produit a base de mousse de chlorure de polyamide et procede de production

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EP (1) EP0194299A1 (fr)
AU (1) AU4809085A (fr)
NO (1) NO843876L (fr)
WO (1) WO1986002036A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995007812A1 (fr) * 1993-09-15 1995-03-23 Polynor Partners As Procede pour la fabrication de produits en plastique alveolaire leger avec alveoles fermees

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4434251A (en) * 1980-06-04 1984-02-28 The Furukawa Electric Co., Ltd. Cross-linked polyvinyl chloride resin foam and method of manufacturing the same

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4434251A (en) * 1980-06-04 1984-02-28 The Furukawa Electric Co., Ltd. Cross-linked polyvinyl chloride resin foam and method of manufacturing the same

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995007812A1 (fr) * 1993-09-15 1995-03-23 Polynor Partners As Procede pour la fabrication de produits en plastique alveolaire leger avec alveoles fermees
AU680687B2 (en) * 1993-09-15 1997-08-07 Polynor Partners As Process for the production of products of light cellular plastic with closed cells
US5667740A (en) * 1993-09-15 1997-09-16 Polynor Partners A/S Process for the production of products of light cellular plastic with closed cells
RU2124531C1 (ru) * 1993-09-15 1999-01-10 Полюнор Партнерс АС Способ производства изделий из легкого поропласта с закрытыми порами
CN1054099C (zh) * 1993-09-15 2000-07-05 波利诺合伙人有限公司 制备闭孔的轻质多孔塑料制品的方法

Also Published As

Publication number Publication date
NO843876L (no) 1986-04-01
EP0194299A1 (fr) 1986-09-17
AU4809085A (en) 1986-04-17

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