GB1562026A - Styrene polymer foam and preparation thereof - Google Patents
Styrene polymer foam and preparation thereof Download PDFInfo
- Publication number
- GB1562026A GB1562026A GB3097877A GB3097877A GB1562026A GB 1562026 A GB1562026 A GB 1562026A GB 3097877 A GB3097877 A GB 3097877A GB 3097877 A GB3097877 A GB 3097877A GB 1562026 A GB1562026 A GB 1562026A
- Authority
- GB
- United Kingdom
- Prior art keywords
- blowing agent
- pph
- foam body
- patent specification
- styrene polymer
- 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.)
- Expired
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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
- C08J9/04—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
- C08J9/12—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 physical blowing agent
- C08J9/14—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 physical blowing agent organic
- C08J9/143—Halogen containing compounds
- C08J9/144—Halogen containing compounds containing carbon, halogen and hydrogen only
-
- 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
- C08J2325/00—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 an aromatic carbocyclic ring; Derivatives of such polymers
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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)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Description
(54) STYRENE POLYMER FOAM AND PREPARATION THEREOF
(71) We, THE DOW CHEMICAL COMPANY, a Corporation organised and existing under the laws of the State of Delaware, United States of America, of Midland, County of
Midland, State of Michigan, United States of America, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:
This invention relates to styrene polymer foam bodies and processes for their production.
One of the major applications for styrene polymer foams is in the field of thermal insulation. A styrene polymer foam for thermal insulation desirably has relatively small cells and excellent dimensional stability. It is also highly desirable that the insulating value of the foam be maintained for as long as possible. From a processing standpoint, certain halogencontaining compounds such as dichlorodifluoromethane, have been found to be useful in preparing extruded styrene polymer foams. At the present time it is believed that such compounds, when released into the atmosphere, may reduce the effectiveness of the ozone layer as a solar shield. Therefore, it would be desirable generally to eliminate such compounds from applications where ultimately they are released to the atmosphere.
In our U.K. Patent Specification No. 1537421 we have described and claimed a styrene polymer (as herein defined) elongate foam body having a machine direction and a transverse direction, and defining a plurality of closed cells containing at least one blowing agent which is a compound of formula:
R1 - CF2 - R2 (1) in which R1 is methyl, ethyl, chloromethyl, fluoromethyl, chlorofluoromethyl, difluoromethyl or trifluoromethyl, and R2 is hydrogen, chloro, fluoro, trifluoromethyl or methyl, with the proviso that the compound contains not more than 3 carbon atoms, and that if the compound contains only 2 fluorine atoms it must contain 3 carbon atoms, which cells are substantially uniform and have an average cell size of from 0.1 to 1.2 millimetres, the foam body having a cross-sectional area of at least 8 square inches, a cross-sectional dimension of at least 0.25 inch, a water vapour permeability not greater than 1.8 perm inches as measured by ASTM Method C 355-64 Procedures for Desiccant Method, and a density of from 1 to 5 pounds per cubic foot.
In our U.K. Patent Specification No. 1537421 we have also described and claimed a process for making such a foam body, which process comprises extruding a styrene polymer stream containing a mixture of at least one first blowing agent which is a compound of formula (I) as defined above and at least one second blowing agent having a permeability through the polymer of greater than 0.017 times that of nitrogen.
We have now found that the objects of the invention disclosed in our U.K. Patent
Specification No. 1537421 can also be achieved by using as the or a blowing agent in preparing extruded styrene polymer foams a compound of formula (I) as defined above in which R1 is dichloromethyl, i.e. a compound selected from: CCl2H - CF3, CC12H - CF2 - CF3, and CCl2H - CF2 - CH3.
According to the present invention, therefore, there is provided a modification of the styrene polymer elongate foam body as claimed in any one of claims 1 to 5 of U.K. Patent
Specification No. 1537421 in which in the formula: R1-CF2-R2 (I),
R1 is dichloromethyl.
As well as containing one or more compounds of formula (I) as defined above in which R1 is dichloromethyl the cells may further contain at least one blowing agent which is a compound of formula (I) as defined in claim 1 of U.K. Patent Specification No. 1537421.
1,1, 1-Trifluoropropane, 2,2-difluoropropopane, 1,1,2,2-tetrafluoroethane; 1,1,1,2tetrafluoro-2-chloroethane; 1,1, 1-trifluoro-2-chloroethane; pentafluoroethane; 1,1,2trifluoroethane; 1,1, 1-trifluorethane; octafluoropropane; and l,l-difluoro-l-chloroethane, in particular, have been found useful as the additional blowing agent(s).
In preferred embodiments, the styrene polymer foam body has one or both of the following properties:
(a) an average cell size of from 0.1 to 0.9 millimetres; and
(b) a thermal conductivity at least 0.03 British Thermal Units-inch per hour per square foot per "F less than a like body in which the cells contain only air.
The term "styrene polymer" refers to a solid polymer of one or more polymerizable alkenyl aromatic compounds. The homopolymer or copolymer comprises in chemically combined form, at least 70 percent by weight of at least one alkenvl aromatic comnound having the general formula
wherein Ar is an aromatic hydrocarbon radical, or an aromatic halo-hydrocarbon radical of the benzene series, and R is hydrogen or the methyl radical.Examples of such polymers are the solid homopolymers of styrene, a-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstryene, ar-ethylstyrene, ar-vinylxylene, ar-chlorostyrene and ar-bromostyrene, and the solid copolymers of two or more of such alkenyl aromatic compounds with minor amounts of other readily co-polymerizable olefinic compounds such as, for example, methylmethacrylate, acrylonitrile, maleic anhydride, citraconic anhydride, itaconic anhydride, acrylic acid, and rubber reinforced (either natural or synthetic) styrene polymers.
The foam bodies according to the invention are made by a modification of the process as claimed in any one of claims 6 to 9 of U.K. Patent Specification No. 1537421 in which in the formula: R1 - CF2 - R2 (1), R1 is dichloromethyl. The first blowing agent component of the styrene polymer stream may further comprise at least one blowing agent of formula (I) as defined in claim 1 of U.K. Patent
Specification No. 1537421.
The second blowing agent or agents have a permeability such that the amount retained in the cells becomes vanishingly small. When first prepared both first and second blowing agents will be in the cells. However, within a short time, depending on blowing agent and cell wall thickness, most of the second blowing agent will have diffused out of the cells.
Suitable such second blowing agents include fluorochloromethane, methyl chloride, ethyl chloride, chlorodifluoromethane and 1, 1-difluoroethane.
Preferably, the mixture of first and second blowing agents comprises from 30 to 70 weight percent of the first blowing agent(s).
Typically, the foam bodies of the invention are made by first injecting a mixture of the first and second blowing agents into a heat-plastified styrene polymer stream within an extruder.
From the extruder the heat-plastified gel is passed into a mixer, the mixer being a rotary mixer wherein a studded rotor is enclosed within a housing which has a studded internal surface which intermeshes with the studs on the rotor. The heat-plastified gel is fed from the extruder into the inlet end of the mixer and discharged from the outlet end, the flow being in a generally axial direction. From the mixer, the gel passes through coolers and from the coolers to a die which extrudes a generally rectangular board.
In the preparation of foams in accordance with the present invention, it is often desirable to add a nucleating agent, such as, for example, talc, calcium silicate, or indigo, to reduce the cell size.
In order that the invention may be more fully understood, the following Examples are given by way of illustration only. Examples 1 to 3 are comparative examples and Example 4 is in accordance with the present invention.
EXAMPLES 1 to 4
In each of the following Examples a stream of polystyrene containing 3 parts per 100 parts (pph) of commercial monochloropentabromocyclohexane (flame retarding agent), 0.075 pph of barium stearate, 0.03 pph magnesium oxide and a nucleating agent was fed to an extrusion assembly. Into each of the streams was injected continuously one or more blowing agents. At foaming temperatures of from 104 to 1050C, polystyrene foam was extruded as a rectangular board having a cross-sectional dimensions of 1 in x 10 in.
The feed rates, blowing agent composition (in percent by weight) and physical properties of the extrudate are set forth in the Table below. Density is shown in pounds per cubic foot (pcf) and grams/litre, and cell size in millimetres (mm). All concentrations designated as parts per hundred (pph) are parts by weight per 100 parts of polystyrene.
Blowing Agent Foaming Density Cell Size
Ex. Blowing Agent Conc. (pph) Temp. pcf(g/l) {mum) 1 CH3Cl 10 1050C 4.6 ( 73.6) 6.5
2 CH3Cl 14 1040C 2.6 ( 41.6) 4.6
3 CHC12CF3 34.4 1050C 8.8 (140.8) 6.5
4 50/50 16 1050C 2.3( 36.8) 0.4
CHC13/CHC12CF3
WHAT WE CLAIM IS:
1. A modification of the styrene polymer elongate foam body as claimed in any one of claims 1 to 5 of U.K. Patent Specification No. 1537421 in which in the formula: Rl - CF2 - R2 (I) Rl is dichloromethyl.
2. A foam body as claimed in claim 1 in which the cells further contain at least one blowing agent as defined in claim 1 of U.K. Patent Specification No. 1537421.
3. A foam body as claimed in claim 2 in which the additional blowing agent is 1,1difluoro- 1 -chloroethane.
4. A foam body as claimed in claim 1 substantially as hereinbefore described in Example 4.
5. A modification of the process as claimed in any one of claims 6 to 9 of U.K. Patent
Specification No. 1537421 in which in the formula: RI -CF2-R2 (1), R1 is dichloromethyl.
6. A process as claimed in claim 5 in which the first blowing agent component of the styrene polymer stream further comprises at least one blowing agent as defined in claim 1 of
U.K. Patent Specification No. 1537421.
7. A process as claimed in claim 6 in which the additional blowing agent is 1,1 - difluoro 1 - chloroethane.
8. A process as claimed in claim 5 substantially as hereinbefore described in Example 4.
9. A foam body which has been made by the process claimed in any one of claims 5 to 8.
**WARNING** end of DESC field may overlap start of CLMS **.
Claims (9)
- **WARNING** start of CLMS field may overlap end of DESC **.EXAMPLES 1 to 4 In each of the following Examples a stream of polystyrene containing 3 parts per 100 parts (pph) of commercial monochloropentabromocyclohexane (flame retarding agent), 0.075 pph of barium stearate, 0.03 pph magnesium oxide and a nucleating agent was fed to an extrusion assembly. Into each of the streams was injected continuously one or more blowing agents. At foaming temperatures of from 104 to 1050C, polystyrene foam was extruded as a rectangular board having a cross-sectional dimensions of 1 in x 10 in.The feed rates, blowing agent composition (in percent by weight) and physical properties of the extrudate are set forth in the Table below. Density is shown in pounds per cubic foot (pcf) and grams/litre, and cell size in millimetres (mm). All concentrations designated as parts per hundred (pph) are parts by weight per 100 parts of polystyrene.Blowing Agent Foaming Density Cell Size Ex. Blowing Agent Conc. (pph) Temp. pcf(g/l) {mum) 1 CH3Cl 10 1050C 4.6 ( 73.6) 6.52 CH3Cl 14 1040C 2.6 ( 41.6) 4.63 CHC12CF3 34.4 1050C 8.8 (140.8) 6.54 50/50 16 1050C 2.3( 36.8) 0.4 CHC13/CHC12CF3 WHAT WE CLAIM IS: 1. A modification of the styrene polymer elongate foam body as claimed in any one of claims 1 to 5 of U.K. Patent Specification No. 1537421 in which in the formula: Rl - CF2 - R2 (I) Rl is dichloromethyl.
- 2. A foam body as claimed in claim 1 in which the cells further contain at least one blowing agent as defined in claim 1 of U.K. Patent Specification No. 1537421.
- 3. A foam body as claimed in claim 2 in which the additional blowing agent is 1,1difluoro- 1 -chloroethane.
- 4. A foam body as claimed in claim 1 substantially as hereinbefore described in Example 4.
- 5. A modification of the process as claimed in any one of claims 6 to 9 of U.K. Patent Specification No. 1537421 in which in the formula: RI -CF2-R2 (1), R1 is dichloromethyl.
- 6. A process as claimed in claim 5 in which the first blowing agent component of the styrene polymer stream further comprises at least one blowing agent as defined in claim 1 of U.K. Patent Specification No. 1537421.
- 7. A process as claimed in claim 6 in which the additional blowing agent is 1,1 - difluoro 1 - chloroethane.
- 8. A process as claimed in claim 5 substantially as hereinbefore described in Example 4.
- 9. A foam body which has been made by the process claimed in any one of claims 5 to 8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB3097877A GB1562026A (en) | 1977-07-22 | 1977-07-22 | Styrene polymer foam and preparation thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB3097877A GB1562026A (en) | 1977-07-22 | 1977-07-22 | Styrene polymer foam and preparation thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| GB1562026A true GB1562026A (en) | 1980-03-05 |
Family
ID=10316077
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB3097877A Expired GB1562026A (en) | 1977-07-22 | 1977-07-22 | Styrene polymer foam and preparation thereof |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB1562026A (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2125796A (en) * | 1982-08-23 | 1984-03-14 | Cosden Technology | Flame retarding extruded plastics foam compositions |
| US4947881A (en) * | 1989-02-24 | 1990-08-14 | Allied-Signal Inc. | Method of cleaning using hydrochlorofluorocarbons |
| EP0392668A1 (en) * | 1989-04-10 | 1990-10-17 | E.I. Du Pont De Nemours And Company | Azeotrope-like mixtures of 1,1-dichloro-2,2,2-trifluoroethane and 1,1,-dichloro-1-fluoroethane |
| US4988455A (en) * | 1989-10-06 | 1991-01-29 | Allied-Signal Inc. | Azeotrope-like compositions of 1,1-dichloro-1,2,2-trifluoropropane and alkanol having 1 to 4 carbon atoms |
| WO1991005082A1 (en) * | 1989-10-06 | 1991-04-18 | Allied-Signal Inc. | Azeotrope-like compositions of dichloropentafluoropropane and 1,2-dichloroethylene |
| WO1991013934A1 (en) * | 1990-03-12 | 1991-09-19 | E.I. Du Pont De Nemours And Company | Ternary azeotropic compositions of dichloropentafluoropropane and trans-1,2-dichloroethylene with methanol or ethanol or isopropanol |
| US5104565A (en) * | 1990-06-25 | 1992-04-14 | Allied-Signal Inc. | Azeotrope-like compositions of dichloropentafluoropropane, 2-propanol and a hydrocarbon containing six carbon atoms |
| US5106526A (en) * | 1990-06-06 | 1992-04-21 | Allied-Signal Inc. | Azeotrope-like compositions of dichloropentafluoropropane, methanol and a hydrocarbon containing six carbon atoms |
| US5116526A (en) * | 1989-10-06 | 1992-05-26 | Allied-Signal Inc. | Azeotrope-like compositions of dichloropentafluoropropane and 1,2-dichloroethylene |
| US5118437A (en) * | 1989-12-21 | 1992-06-02 | Allied-Signal Inc. | Azeotrope-like compositions of dichloropentafluoropropane, ethanol and a hydrocarbon containing six carbon atoms |
| US5124065A (en) * | 1989-10-06 | 1992-06-23 | Allied-Signal Inc. | Azeotrope-like compositions of dichloropentafluoropropane and an alkanol having 1-4 carbon atoms |
| US5320683A (en) * | 1989-02-06 | 1994-06-14 | Asahi Glass Company Ltd. | Azeotropic or azeotropic-like composition of hydrochlorofluoropropane |
| US5607912A (en) * | 1989-02-01 | 1997-03-04 | Asahi Glass Company Ltd. | Hydrochlorofluorocarbon azeotropic or azeotropic-like mixture |
-
1977
- 1977-07-22 GB GB3097877A patent/GB1562026A/en not_active Expired
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2125796A (en) * | 1982-08-23 | 1984-03-14 | Cosden Technology | Flame retarding extruded plastics foam compositions |
| US5607912A (en) * | 1989-02-01 | 1997-03-04 | Asahi Glass Company Ltd. | Hydrochlorofluorocarbon azeotropic or azeotropic-like mixture |
| US5320683A (en) * | 1989-02-06 | 1994-06-14 | Asahi Glass Company Ltd. | Azeotropic or azeotropic-like composition of hydrochlorofluoropropane |
| US4947881A (en) * | 1989-02-24 | 1990-08-14 | Allied-Signal Inc. | Method of cleaning using hydrochlorofluorocarbons |
| AU629625B2 (en) * | 1989-04-10 | 1992-10-08 | E.I. Du Pont De Nemours And Company | Azeotrope-like mixtures of 1,1-dichloro-2,2,2- trifluoroethane and 1,1-dichloro-1-fluoroethane |
| EP0392668A1 (en) * | 1989-04-10 | 1990-10-17 | E.I. Du Pont De Nemours And Company | Azeotrope-like mixtures of 1,1-dichloro-2,2,2-trifluoroethane and 1,1,-dichloro-1-fluoroethane |
| US4988455A (en) * | 1989-10-06 | 1991-01-29 | Allied-Signal Inc. | Azeotrope-like compositions of 1,1-dichloro-1,2,2-trifluoropropane and alkanol having 1 to 4 carbon atoms |
| WO1991005082A1 (en) * | 1989-10-06 | 1991-04-18 | Allied-Signal Inc. | Azeotrope-like compositions of dichloropentafluoropropane and 1,2-dichloroethylene |
| US5288819A (en) * | 1989-10-06 | 1994-02-22 | Alliedsignal Inc. | Azeotrope-like compositions of dichloropentafluoropropane and 1,2-dichloroethylene |
| US5116526A (en) * | 1989-10-06 | 1992-05-26 | Allied-Signal Inc. | Azeotrope-like compositions of dichloropentafluoropropane and 1,2-dichloroethylene |
| US5124065A (en) * | 1989-10-06 | 1992-06-23 | Allied-Signal Inc. | Azeotrope-like compositions of dichloropentafluoropropane and an alkanol having 1-4 carbon atoms |
| US5118437A (en) * | 1989-12-21 | 1992-06-02 | Allied-Signal Inc. | Azeotrope-like compositions of dichloropentafluoropropane, ethanol and a hydrocarbon containing six carbon atoms |
| WO1991013934A1 (en) * | 1990-03-12 | 1991-09-19 | E.I. Du Pont De Nemours And Company | Ternary azeotropic compositions of dichloropentafluoropropane and trans-1,2-dichloroethylene with methanol or ethanol or isopropanol |
| US5106526A (en) * | 1990-06-06 | 1992-04-21 | Allied-Signal Inc. | Azeotrope-like compositions of dichloropentafluoropropane, methanol and a hydrocarbon containing six carbon atoms |
| US5104565A (en) * | 1990-06-25 | 1992-04-14 | Allied-Signal Inc. | Azeotrope-like compositions of dichloropentafluoropropane, 2-propanol and a hydrocarbon containing six carbon atoms |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PS | Patent sealed | ||
| 429A | Application made for amendment of specification (sect. 29/1949) | ||
| 429H | Application (made) for amendment of specification now open to opposition (sect. 29/1949) | ||
| 429D | Case decided by the comptroller ** specification amended (sect. 29/1949) | ||
| SP | Amendment (slips) printed | ||
| PE20 | Patent expired after termination of 20 years |
Effective date: 19970130 |