DK156442B - PROCEDURE FOR MANUFACTURING HARD FOAMSTUFF MATERIALS BASED ON POLYVINYL CHLORIDE - Google Patents
PROCEDURE FOR MANUFACTURING HARD FOAMSTUFF MATERIALS BASED ON POLYVINYL CHLORIDE Download PDFInfo
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- DK156442B DK156442B DK005177AA DK5177A DK156442B DK 156442 B DK156442 B DK 156442B DK 005177A A DK005177A A DK 005177AA DK 5177 A DK5177 A DK 5177A DK 156442 B DK156442 B DK 156442B
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- 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
- C08J9/36—After-treatment
-
- 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
Description
DK 156442BDK 156442B
Opfindelsen angâr en fremgangsmâde til fremstil-ling af hârde skumformstofmaterialer pâ basi's af polyvinylchlorid, hvor en blanding af polyvinylchlorid, skummemiddel og temporært blodgoringsmiddel opvarmes, 5 afkoles og ekspanderes, og fremgangsmâden er ejendomme-lig ved at der som temporært blodgoringsmiddel anvendes en polymeriserbar monomer med mindst én ethylenisk u-mættet dobbeltbinding, hvorhos blandingen opvarmes under tryk i en trykform og afkoles, det sâledes opnâede for-10 mede legeme fjernes fra formen, opvarmes for at medfore ekspansion, og den polymeriserbare monomer, efter fuld-fort ekspansion, polymeriseres ved hjælp af ioniserende strâling, idet den ioniserende strâling er ultraviolette strâler, rontgenstrâler, gammastrâler, betapartikler 15 eller accelererede elektronstrâler.The invention relates to a process for the preparation of hard foam resin materials on the basis of polyvinyl chloride, wherein a mixture of polyvinyl chloride, foaming agent and temporary anticoagulant is heated, cooled and expanded, and the method is characterized by the use of a temporary antifoaming agent. at least one ethylenically unsaturated double bond wherein the mixture is heated under pressure in a printing mold and cooled, the resulting body obtained so from the mold is heated to cause expansion, and the polymerizable monomer, after full expansion, is polymerized by by means of ionizing radiation, the ionizing radiation being ultraviolet, X-ray, gamma, beta particles or accelerated electron beams.
Det er kendt at fremstille hârde skumstoffer ud fra polyvinylchlorid. Herved bliver en blanding af polyvinylchlorid, skummemiddel og oplosningsmiddel, sâsom acetone eller toluen, der tjener som temporært blodg®-20 ringsmiddel, forarbejdet i trykforme eller ved ekstru-dering eller sprojtestobning og derefter opskummet. Efter gennemfort opskumning skal oplosningsmidlet fjernes ved fordampning. Dette arbejdstrin er meget arbejdskræ-vende og miljobelastende.It is known to produce hard foams from polyvinyl chloride. Hereby, a mixture of polyvinyl chloride, foaming agent and solvent, such as acetone or toluene serving as a temporary antifouling agent, is processed in pressurized form or by extrusion or injection molding and then foamed. After foaming, the solvent should be removed by evaporation. This work step is very labor intensive and environmentally damaging.
25 Det er ogsà kendt at benytte monomère, sâsom isocyanater, diisocyanater eller methylmethacrylat, som temporært blodgoringsmiddel (C.Y. Benning, Plastic Fo-ams, Wiley-Interscience 1969, side 112 og 115).25 It is also known to use monomers, such as isocyanates, diisocyanates or methyl methacrylate, as a temporary blood-gelling agent (C.Y. Benning, Plastic Foams, Wiley-Interscience 1969, pages 112 and 115).
Disse monomère bliver under fremstillingsproces-30 sen, og sâledes ogsâ under opskumningen, omdannet til hârde polymère produkter ved indvirkning af vand (ved isocyanat og diisocyanat) eller ved indvirkning af ra-dikalinitiatorer.These monomers are transformed into hard polymeric products by the action of water (by isocyanate and diisocyanate) or by the action of radical initiators during the manufacturing process, and thus also during the foaming.
Navnlig ved anvendelse af methylmethacrylat er 35 det, pâ grund af den under varmeindvirkningen begynden-de polymérisation, der udloses af radikalinitiatorer,In particular, using methyl methacrylate, due to the heat initiation polymerization triggered by radical initiators,
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2 vanskeligt at opnâ en god ensartet og tilstrækkelig ekspansion. Den monomère polymeriseres for hurtigt, sâ-ledes at den blodgorende virkning, der er nodvendig for en god ekspansion, for hurtigt gâr tabt.2 difficult to achieve a good uniform and sufficient expansion. The monomer is polymerized too quickly, causing the blood-borne action necessary for good expansion to be lost too quickly.
5 Den foreliggende opfindelse har til formai at afhjælpe ulemper ved den tidligere teknik og at opnâ fordele sammenlignet med denne, for eksempel sammen-lignet med, hvad der er kendt fra britisk patentskrift nr. 1.219.803, der beskriver en fremgangsmâde af lig-10 nende art som den foreliggende.The present invention aims to alleviate disadvantages of the prior art and to obtain advantages over it, for example, as compared to what is known from British Patent Specification No. 1,219,803, which discloses a method of equation 10 such as the present one.
Det karakteristiske ved den foreliggende opfindelse sammenlignet med, hvad der er kendt fra britisk patentskrift nr. 1.219.803 er folgende:The characteristic of the present invention compared to what is known from British Patent Specification No. 1,219,803 is as follows:
Den foreliggende opfindelse angâr en frem-15 gangsmâde til fremstilling af harde skumprodukter pâ basis af PVC, hvor mindst 98% af aile celler er lukket, og hertil anvendes sâkaldte "temporære" blodgoringsmid-ler, der har den opgave at gore det relativt hârde PVC opskummeligt. Disse "temporære" blodgoringsmidler poly-20 meriseres ved bestrâlingen af de færdigfremstillede cellelegemer ved hjælp af ioniserende strâler og brin-ges sâledes til at "forsvinde" pâ en absolut miljoven-lig mâde.The present invention relates to a process for the production of PVC hard foam products in which at least 98% of all cells are closed, and so-called "temporary" blood softening agents are used, which have the task of making the relatively hard PVC intumescent. These "temporary" blood softeners are polymerized by the irradiation of the finished cell bodies by ionizing rays and are then "disappeared" in an absolutely environmentally friendly manner.
Det fra britisk patentskrift nr. 1.219.803 kend-25 te adskiller sig fra det foregâende ved f0lgende: a) Eksemplerne i nævnte patentskrift resulterer i blode til halvblode skum.British Patent Specification No. 1,219,803 is distinguished from the foregoing by the following: a) The examples of said patent result in blood to semi-blood foam.
b) Harpikskomponenterne, der udgores af bled PVC, 30 skal til forbedring af opskumningsegenskaberne fortværbindes for ekspansionen ved hjælp af be-strâling og forst derefter kan cellelegemet frem-stilles (opskummes).b) The resin constituents made of soft PVC must, for enhancing the foaming properties, be fortified for expansion by irradiation and only then can the cell body be made (foamed).
c) Pâ side 1, Unie 77-79 angives, at et skum alle- 35 rede kan anses for at hâve lukkede celler, nâr 50% eller flere af aile celler er lukket.c) On page 1, Union 77-79, it is stated that a foam can already be considered to have closed cells when 50% or more of all cells are closed.
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Ved fremgangsmâden if0lge opfindelsen opnâs let-tere og sikkert hoje procentandele af lukkede celler pâ en mere miljovenlig mâde.In the method according to the invention, easier and safe high percentages of closed cells are obtained in a more environmentally friendly way.
Som monomère med ethylenisk umættet dobbeltbin-5 ding kan der anvendes vinylchlorid, der er luftformigt ved normaltemperatur, men der anvendes fortrinsvis fly-dende monomer med ethylenisk umættet dobbeltbinding, sâsom acrylsyre, methacrylsyre, lavere alkylestre med 1-8 C-atomer af acryl- og/eller methacrylsyre, sâsom 10 methacrylat, ethylacrylat, butylacrylat, methylmetha-crylat, butylmethacrylat eller alkylhexylacrylat, lavere alkylestere med 1-8 C-atomer af maleinsyre, sâsom monomaleinsyre- og dimaleinsyre-methyl- eller -alkylestre, acrylonitriler, methacrylonitriler, 15 acrylsyre- og/eller methacrylsyreestre af glycoler, sâsom ethylenglycoldimethacrylat, vinylforbindelser, sâsom styren eller divinylbenzen, eller allylforbindel-ser, sâsom diallylphthalater.As monomers with ethylenically unsaturated double bond, vinyl chloride which is gaseous at normal temperature can be used, but liquid monomers with ethylenically unsaturated double bond such as acrylic acid, methacrylic acid, lower alkyl esters having 1-8 C atoms of acrylic are preferably used. and / or methacrylic acid, such as methacrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, butyl methacrylate or alkyl hexyl acrylate, lower alkyl esters with 1-8 C atoms of maleic acid, such as monomaleic acid and dimaleic acid methyl or alkyl esters, acrylonitrile acrylic acid and / or methacrylic acid esters of glycols, such as ethylene glycol dimethacrylate, vinyl compounds such as styrene or divinylbenzene, or allyl compounds such as diallylphthalates.
Som monomer i forbindelse med den foreliggende 20 opfindelse gælder ogsâ en blanding af et forpolymerisat med monomer. Som forpolymerisat kan der benyttes polyacryl- og/eller polymethacrylsyreestre, ABS-polymere, og polymère og blandingspolymere af de oven-nævnte monomère.As a monomer in connection with the present invention, a mixture of a prepolymer monomer also applies. As a prepolymer, polyacrylic and / or polymethacrylic acid esters, ABS polymers, and polymers and blend polymers of the above-mentioned monomers can be used.
25 De monomère udvælges og anvendes ait efter de onskede egenskaber hos det endelige skumstof. Sâledes kan for eksempel rumvægten og sejheden hos skumstoffat varieres. De ved fremgangsmâden ifolge opfindelsen fremstillelige skum er at betragte som lette skumpro-30 dukter med en rumvægt under 200 kg/m3. Der kan imidler-tid ogsâ opnâs rumvægte pâ 50 til 100 kg/m3.25 The monomers are selected and used according to the desired properties of the final foam. Thus, for example, the room weight and toughness of foam drums can be varied. The foams produced by the process according to the invention are considered as light foam products having a weight of less than 200 kg / m 3. However, room weights of 50 to 100 kg / m3 can also be obtained.
En for tidlig uonsket termisk polymérisation kan hindres ved samtidig anvendelse af inhibitorer.Premature unwanted thermal polymerization can be prevented by the simultaneous use of inhibitors.
Det med monomer og kemiske eller fysiske skumme-3 5 midler og i mange tilfælde ogsâ med fyldstoffer, pigmenter og stabilisatorer blandede polyvinylchlorid bli- 4Polyvinyl chloride mixed with monomer and chemical or physical foams and in many cases also with fillers, pigments and stabilizers
DK 156442 BDK 156442 B
ver ved i og for sig kendte fremgangsmâder forarbejdet i trykforme, stempelforme, ekstruderingsapparater eller sprojtestebemaskiner og derefter ekspanderet. Efter endt ekspansion bliver den i skumstoffet foreliggende 5 monomer polymeriseret ved indvirkning af ioniserende strâling.are known per se known processes processed into printing molds, piston molds, extruders or spray testing machines and then expanded. Upon completion of expansion, the 5 monomer present in the foam is polymerized by the action of ionizing radiation.
Som ioniserende strâling kan der anvendes UV-strâler, rontgenstrâler, gammastrâler, beta-partikler eller stærkt accelererede elektronstrâler. Der anvendes 10 fortrinsvis elektronstrâler med en energi mellem 400 og 2000 Kev. strâlingensdosen ligger mellem 3 og 15 mega-rad.As ionizing radiation, UV rays, X-rays, gamma rays, beta particles or highly accelerated electron beams can be used. 10 preferably electron beams with an energy of between 400 and 2000 Kev are used. the radiation dose is between 3 and 15 mega-rad.
Arten af skummemiddel er uden betydning for fremgangsmâden ifolge opfindelsen. Der kan anvendes sâ-15 vel fysiske skummemidler, sâsom nitrogen, fréon eller pentan, som kemiske skummemidler, sâsom azodicarboxa-mid, ammoniumcarbonater, alkalibicarbonater eller sulf-hydrazider.The nature of the foaming agent is irrelevant to the process of the invention. Both physical foams, such as nitrogen, freon or pentane, as chemical foams, such as azodicarboxamide, ammonium carbonates, alkali bicarbonates or sulfhydrazides can be used.
Fremgangsmâden ifelge opfindelsen beskrives nær-20 mere gennem folgende eksempler.The process of the invention is described in more detail by the following examples.
Eksempel 1 100 dele PVC blev blandet med 10 dele CaCC>3, 5 25 dele dibasisk blyphthalat, 20 dele ammoniumbicarbonat og 30 dele methylmethacrylat. Denne masse blev i en trykform ved et tryk pâ 250 kg/cm2 opvarmet til 160°c og holdt en halv time ved denne temperatur. Derefter blev der afkolet, og râproduktet blev udtaget af 30 formen. Ekspansionen af râproduktet blev gennemfort i et torreskab ved ca. 100°C, indtil der var opnâet en vægtfylde pâ 70 kg/m3. Dette færdigekspanderede skum-produkt blev derefter behandlet med accelererede elek-troner med en gennemsnitlig energi pâ 400 Kev 35 (strâlingsintensitet 1-3 megarad/sek.). Herved polyme-riserede methylmethacrylatet. Det færdige skumproduktExample 1 100 parts of PVC were mixed with 10 parts of CaCC> 3, 25 parts of dibasic lead phthalate, 20 parts of ammonium bicarbonate and 30 parts of methyl methacrylate. This mass was heated to 160 ° C in a pressure form at a pressure of 250 kg / cm 2 and kept for half an hour at this temperature. Then, it was cooled and the crude product was removed from the mold. The expansion of the raw product was carried out in a drying cabinet at approx. 100 ° C until a density of 70 kg / m3 was reached. This finished expanded foam product was then treated with accelerated electrons with an average energy of 400 Kev 35 (radiation intensity 1-3 megarad / sec). Thereby, the methyl methacrylate polymerized. The finished foam product
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5 var sejelastisk og havde en rumvægt pâ 70 kg/m3.5 was elastic and had a weight of 70 kg / m3.
Eksempel 2 100 dele PVC 5 10 dele CaC03 3 dele Pb-carbonat 1 del Pb-stearat 10 dele MMA (methylmethacrylat) 0,03 dele hydroquinon 10 Blandingen blev bragt ind i en trykform, og luftformigt nitrogen blev t£lif0rt, indtil der var op-nâet et tryk i formen pâ 2’Œ255 )kPa. Formen blev derefter opvarmet til 150 °C ved et ‘irryk pâ 250 kg/cm2 og holdt ved denne temperatur i 30 mimitter. Efter afk0ling blev 15 râproduktet fjernet og ekspanüeret ved 120°C.Example 2 100 parts PVC 5 10 parts CaCO 3 3 parts Pb carbonate 1 part Pb stearate 10 parts MMA (methyl methacrylate) 0.03 parts hydroquinone 10 The mixture was brought into a pressure form and gaseous nitrogen was added until reached a pressure in the form of 2'255 kPa. The mold was then heated to 150 ° C at a pressure of 250 kg / cm 2 and maintained at this temperature for 30 mimits. After cooling, the crude product was removed and expanded at 120 ° C.
Skumproduktet blev rdeæefter udsat for elektron-strâler (750 kV, 25 mA), hvxœved der foregik hærdning. Strâlingsdosen udgj orde 10 Mrad.The foam product was subsequently exposed to electron beams (750 kV, 25 mA), curing while curing. The radiation dose was 10 Mrad.
.Skumproduktet havde :f0lgende ifyjsiske egenskaber : 20 Vægtf.ylde.: 98 kg/m3The foam product had: the following physical properties: 20 Density: 98 kg / m3
Trykstyrke (DIN .53421): 9,2 kp/cm2Compressive strength (DIN .53421): 9.2 kp / cm2
Varmeledningsevne ved 25°C (DIN 52612): 125,5 J/mh°C Specifik modstand: >1013 ohm.cm.Thermal conductivity at 25 ° C (DIN 52612): 125.5 J / mh ° C Specific resistance:> 1013 ohm.cm.
Vicat-temperatur: 81°C.Vicat temperature: 81 ° C.
2525
Eksempel 3Example 3
100 dele PVC100 parts PVC
5 dele CaC03 6 dele Pb-carbonat 30 50 dele diallylphthalat 45 dele "Porofor ADC/M" (azodicarboxamidskummemiddel fra Bayer AG).5 parts CaCO3 6 parts Pb carbonate 30 50 parts diallyl phthalate 45 parts "Porofor ADC / M" (azodicarboxamide foaming agent from Bayer AG).
Den flydende pasta blev bragt ind i formen og opvarmet til 160°C ved et tryk pâ 250 atmosfærer og 35 holdt ved denne temperatur i 30 minutter. Efter afko-ling blev râproduktet ekspanderet ved 100DC og derefter 6The liquid paste was brought into the mold and heated to 160 ° C at a pressure of 250 atmospheres and kept at this temperature for 30 minutes. After cooling, the crude product was expanded at 100DC and then 6
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bestrâlet med elektronstrâler. Strâlingsdosen udgjorde 15 Mrad.irradiated with electron beams. The radiation dose was 15 Mrad.
Fysiske egenskaber af skumproduktet: Vægtfylde: 96 kg/m3 5 Trykstyrke (DIN 53421): 11 kp/cm2Physical properties of the foam product: Density: 96 kg / m3 5 Compressive strength (DIN 53421): 11 kp / cm2
Varmeledningsevne (DIN 52612): 146 J/mh°C Specifik modstand:>l015 ohm.cm.Thermal conductivity (DIN 52612): 146 J / mh ° C Specific resistance:> l015 ohm.cm.
Vicat-temperatur: >100°C.Vicat temperature:> 100 ° C.
10 Eksempel 4 100 dele PVC 10 dele CoCo3 3 del Pb-carbonat 1 del Pb-stearat 15 50 dele MMA (methylmethacrylat) 0,1 del hydroquinonExample 4 100 parts PVC 10 parts CoCo3 3 parts Pb carbonate 1 part Pb stearate 15 50 parts MMA (methyl methacrylate) 0.1 part hydroquinone
Forarbejdningen foregik som i eksempel 2.The processing took place as in Example 2.
Fysiske egenskaber: Vægtfylde: 70 kg/m3 20 Trykstyrke (DIN 53421): 6,5 kg/cm2 Vicat-temperatur: 8 20 C Skærestyrke: 8,0 kg/cm2Physical properties: Density: 70 kg / m3 20 Compressive strength (DIN 53421): 6.5 kg / cm2 Vicat temperature: 8 20 C Cutting strength: 8.0 kg / cm2
Eksempel 5Example 5
25 100 dele PVC25 100 parts PVC
10 dele CaC03 20 dele MMA (methylmethacrylat) 10 dele ethylenglycoldimethacrylat eller butylacrylat 7 dele Pb-carbonat 30 20 dele NH4HC03 0,08 dele hydroquinon10 parts CaCO3 20 parts MMA (methyl methacrylate) 10 parts ethylene glycol dimethacrylate or butyl acrylate 7 parts Pb carbonate 30 parts NH4HCO3 0.08 parts hydroquinone
Forarbejdningen foregik som i eksempel l.The processing was carried out as in Example 1.
I stedet for elektroner blev der til hærdningen anvendt en gamma-strâlingskilde, og strâlingdosen ud-35 gjorde 8 Mrad.Instead of electrons, a gamma radiation source was used for curing and the radiation dose was 8 Mrad.
Vægtfylden af skumproduktet var 85 kg/m3, nàr der anvendtes ethylenglycoldimethacrylat. Med butylacrylatThe density of the foam product was 85 kg / m 3 when ethylene glycol dimethacrylate was used. With butyl acrylate
Claims (7)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH20276A CH597285A5 (en) | 1976-01-09 | 1976-01-09 | |
| CH20276 | 1976-01-09 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| DK5177A DK5177A (en) | 1977-07-10 |
| DK156442B true DK156442B (en) | 1989-08-21 |
| DK156442C DK156442C (en) | 1990-01-02 |
Family
ID=4181570
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DK005177A DK156442C (en) | 1976-01-09 | 1977-01-06 | PROCEDURE FOR MANUFACTURING HARD FOAMSTUFF MATERIALS BASED ON POLYVINYL CHLORIDE |
Country Status (21)
| Country | Link |
|---|---|
| JP (1) | JPS6033848B2 (en) |
| AT (1) | AT355317B (en) |
| AU (1) | AU504245B2 (en) |
| BE (1) | BE850214A (en) |
| CA (1) | CA1073404A (en) |
| CH (1) | CH597285A5 (en) |
| CS (1) | CS192471B2 (en) |
| DD (1) | DD128267A5 (en) |
| DE (1) | DE2606190A1 (en) |
| DK (1) | DK156442C (en) |
| FI (1) | FI64180C (en) |
| FR (1) | FR2337744A1 (en) |
| GB (1) | GB1510050A (en) |
| IE (1) | IE44243B1 (en) |
| IT (1) | IT1086653B (en) |
| LU (1) | LU76542A1 (en) |
| NL (1) | NL183769C (en) |
| NO (1) | NO147568C (en) |
| SE (1) | SE419094B (en) |
| SU (1) | SU655320A3 (en) |
| YU (1) | YU318776A (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1219803A (en) * | 1967-06-03 | 1971-01-20 | Toray Industries | Cellular foamed products prepared from polymers of vinyl chloride and process for their preparation |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL67872C (en) * | 1948-08-16 | 1951-05-15 | L'equipement Menager Et Industriel E.M.I. | PROCEDURE FOR MANUFACTURE OF PRODUCTS WITH A LARGE NUMBER OF CELLS, AND MOLDED ARTICLES WHOLLY OR PARTLY CONSISTED OF THIS MATERIAL |
| GB716366A (en) * | 1950-09-27 | 1954-10-06 | Expanded Rubber Co Ltd | Improvements in or relating to the production of cellular polyvinyl plastics |
| BE627414A (en) * | 1962-01-22 | |||
| NL299705A (en) * | 1962-10-24 | |||
| US3648834A (en) * | 1967-07-14 | 1972-03-14 | Mayer & Co Inc O | Method of making rigid packages from flexible films and products produced thereby |
| GB1386610A (en) * | 1971-10-21 | 1975-03-12 | Exxon Research Engineering Co | Rigid and semirigid foams and process of making them |
-
1976
- 1976-01-09 CH CH20276A patent/CH597285A5/xx not_active IP Right Cessation
- 1976-02-17 DE DE19762606190 patent/DE2606190A1/en active Granted
- 1976-12-23 IE IE2825/76A patent/IE44243B1/en not_active IP Right Cessation
- 1976-12-28 NL NLAANVRAGE7614489,A patent/NL183769C/en not_active IP Right Cessation
- 1976-12-30 GB GB54299/76A patent/GB1510050A/en not_active Expired
- 1976-12-30 YU YU03187/76A patent/YU318776A/en unknown
- 1976-12-30 FI FI763748A patent/FI64180C/en not_active IP Right Cessation
- 1976-12-30 AT AT984876A patent/AT355317B/en not_active IP Right Cessation
- 1976-12-31 CS CS768898A patent/CS192471B2/en unknown
-
1977
- 1977-01-04 SE SE7700071A patent/SE419094B/en not_active IP Right Cessation
- 1977-01-06 DK DK005177A patent/DK156442C/en not_active IP Right Cessation
- 1977-01-06 DD DD7700196840A patent/DD128267A5/en unknown
- 1977-01-07 LU LU76542A patent/LU76542A1/xx unknown
- 1977-01-07 FR FR7700357A patent/FR2337744A1/en active Granted
- 1977-01-07 AU AU21150/77A patent/AU504245B2/en not_active Expired
- 1977-01-07 NO NO770050A patent/NO147568C/en unknown
- 1977-01-07 IT IT47543/77A patent/IT1086653B/en active
- 1977-01-07 SU SU772435955A patent/SU655320A3/en active
- 1977-01-07 BE BE173943A patent/BE850214A/en not_active IP Right Cessation
- 1977-01-08 JP JP52001111A patent/JPS6033848B2/en not_active Expired
- 1977-01-10 CA CA269,428A patent/CA1073404A/en not_active Expired
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1219803A (en) * | 1967-06-03 | 1971-01-20 | Toray Industries | Cellular foamed products prepared from polymers of vinyl chloride and process for their preparation |
Also Published As
| Publication number | Publication date |
|---|---|
| YU318776A (en) | 1982-05-31 |
| IE44243L (en) | 1977-07-09 |
| FR2337744B1 (en) | 1981-03-27 |
| SU655320A3 (en) | 1979-03-30 |
| DD128267A5 (en) | 1977-11-09 |
| IE44243B1 (en) | 1981-09-23 |
| LU76542A1 (en) | 1977-07-15 |
| ATA984876A (en) | 1979-07-15 |
| FI64180C (en) | 1983-10-10 |
| FR2337744A1 (en) | 1977-08-05 |
| IT1086653B (en) | 1985-05-28 |
| CS192471B2 (en) | 1979-08-31 |
| DK156442C (en) | 1990-01-02 |
| CH597285A5 (en) | 1978-03-31 |
| NL183769C (en) | 1989-01-16 |
| AU2115077A (en) | 1978-07-13 |
| DE2606190C2 (en) | 1987-02-26 |
| CA1073404A (en) | 1980-03-11 |
| SE419094B (en) | 1981-07-13 |
| NO770050L (en) | 1977-07-12 |
| NO147568B (en) | 1983-01-24 |
| JPS6033848B2 (en) | 1985-08-05 |
| DE2606190A1 (en) | 1977-07-21 |
| DK5177A (en) | 1977-07-10 |
| NL183769B (en) | 1988-08-16 |
| FI763748A (en) | 1977-07-10 |
| AT355317B (en) | 1980-02-25 |
| JPS5287467A (en) | 1977-07-21 |
| BE850214A (en) | 1977-07-07 |
| AU504245B2 (en) | 1979-10-04 |
| FI64180B (en) | 1983-06-30 |
| NO147568C (en) | 1983-05-04 |
| NL7614489A (en) | 1977-07-12 |
| GB1510050A (en) | 1978-05-10 |
| SE7700071L (en) | 1977-07-10 |
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