JPS60135439A - Manufacture of styrene polymer foamed body and foamed body thereby - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION One of the major uses of styrene polymer extrusions is in the field of thermal insulation. Heaters suitable for thermal insulation are desirable to have relatively small cells and long-term dimensional stability and insulation values.

The styrene polymer foams contemplated within the scope of this invention are extruded foams. Such extruded foams have fairly uniform cell dimensions. They are also used in the field of decorative decoration.

%i/([Preferred stable styrene polymer solids are obtained using the method of Nakamura U.S. Pat. No. 3,960,792 using methyl chloride or a mixture of methyl chloride and chlorofluorocarbon as the blowing agent. When using such a system, the emulsion must be aged for an extended period of time to allow methyl chloride to leave the cell and air to enter by suitable diffusion methods through the cell walls. The aging time of the boards creates inconvenient storage problems.

Due to the extremely difficult physical properties of crushed methylene chloride, care must be taken to ensure good ventilation when cutting such bodies into moldings.

The extruded foam and its method of manufacture are disclosed in the following US patents: Ha2,4+19,910;2.
,515,250:2.669,751 ;2,848
,428 :2,928,130 ;:(,121,1
30;:(,12L,911;3,770,688;:
3,815,674;3,960.792:3,96
6.381; 4.0 B 5,073 and 4,14
It has now been discovered that methyl chloride as a blowing agent for 6,563° extruded polystyrene inventions can be replaced with a deforming agent selected from the group consisting of: However, all of the 6 percentages (%) below are based on Reijun Shigetoshi.

(1) Approximately 5-20% isopropyl alcohol and 5-20% isopropyl alcohol
50% chlorodifluoromethane and 30-70% dichlorodifluoromethane; Difluoromethane; and mixtures thereof.

Also contemplated within the scope of this invention are synthetic resin thermoformed extrusions made by the above-described method. However, in this case, an elongated envelope of alkenyl aromatic thermoplastic synthetic resin has a machine direction and a transverse direction, and the expander forms inside a large number of closed, non-interconnected gas-containing cells. The cells have an average cell size of about 0.1 to 1.2 ms, preferably 0.1 to 0.9 m, and the emitter is of a uniform cell structure with no discontinuities and has a minimum cross-sectional dimension of the emitter. by the average cell diameter across (i.e., for example ASTM
The foam has no substantial variation in average cell size when the cell size is measured (by Method D-2842-69) and the elongated foam has at least 51.6 cJ (8 square inches).
cross-sectional area of and at least 0.64 cm I O,25
The foam has a minimum cross-sectional dimension of 3.0 cm (1.8 cm) or less as measured by the procedure of Desiccant AST Ivi Method C355-64. The W of the embryo is approximately 16-90.
h/m 311-5 bonds/cubic foot), and furthermore the cell is a mountain as an excavator whose transmittance through the alkenyl aromatic resin polymer is less than 0017 times the transmittance of nitrogen through the emitter. Contains Ca monohydric alcohol, and blowing agent is 0.12 W/m/'C■)
, 08 pod country heat-eating unit/inch/hr/ft2/
y) has the following heat transfer of 4 degrees.

"Alkenyl aromatic synthetic resin" is defined as at least one compound having the following general formula (in which Ar is an aromatic hydrocarbon or halohydrocarbon group, and R is hydrogen or methyl). means a solid polymer of 1 fl or more of a polymerizable alkenyl aromatic compound containing at least 70% by weight of an alkenyl aromatic compound in chemically bound form. Examples of such alkenyl aromatic resins is styrene, a-methylstyrene, 0-methylstyrene,
solid homopolymers of In-methylstyrene, In-methylstyrene, p-methylstyrene, al-ethylstyrene, al-vinylxylene, blue chlorostyrene or al-bromostyrene; one or more of these more alkenyl aromatics solid copolymers of the compound with other readily polymerizable olefinic compounds (e.g. methyl methacrylate, acrylonitrile, maleic anhydride, citraconic anhydride, iconic anhydride, acrylic/L-acid); rubber reinforcement (natural or synthetic) styrene polymers, etc.

Blowing agents useful in the practice of this invention may be of commercial purity, and are generally satisfactory. However, modified ethyl alcohol is available in a wide variety of formulations, and modification is accomplished by adding everything from methanol to low volatility materials such as hard soaps and sulfuric acid. In order to be suitable for carrying out the present invention,
Such denatured alcohols should generally be non-corrosive to the processing equipment or to the environment in which the foam is to be used. Furthermore, the denatured alcohol should not unduly lower the heat distortion temperature of the foam. To determine whether a particular denatured alcohol is suitable, the alcohol is incorporated into the desired polymer at 1% by weight, based on the weight of the polymer, and the mixture is injection molded. The injection molded specimen is held under pressure until it solidifies to prevent foaming of the specimen. The V-cut heat distortion temperature of the molded samples is then measured according to ASTM (American Society Testing Materials) test D-1525-76. A similar injection molding is performed using the polymer without denatured alcohol and its Vicat thermal deformation is similarly measured. An alcohol is satisfactory for the practice of the present invention if the heat distortion temperature of a sample containing 1 g of denatured alcohol is no more than 7°C lower than the heat distortion temperature of a sample without alcohol.

Representative suitable denatured alcohols include, on a weight basis, the following:

■ 85.8% Ethyl alcohol 4.3% Wood spirit alcohol 4.5% Methanol 4.5% Inglobil alcohol 0.9% Methylibutyl ketone @ 89.9% Ethyl alcohol 4.5% Methanol 4.7% Ethyl acetate 0.9% Methyl isobutyl ketone (3) 82.1% Ethyl alcohol 17% Methanol 0.9% Methyl isobutyl ketone (leakage) 95°2% Ethyl alcohol 1% Kerosene 3.8% Vicat heat of methyl isobutyl ketone polymer A wide range of other modified ethyl alcohol formulations that do not unduly reduce the distortion temperature can also be used.Up to 25% of the modifying material can be used if the ethyl alcohol formulation complies with the heat distortion requirements described above. can do.

In general, the preparation of alkenyl aromatic resin polymer foams is most conveniently carried out by methods such as those described in US Pat. No. 2,669.751. That is, therein a volatile fluid blowing agent is injected into the plasticized polymer stream within the extruder. The thermoplastic gel from the extruder passes through a mixer.

The mixer is a rotary mixer with a studded rotor within a housing having a studded inner surface that interlocks with studs on the rotor. The thermoplastic gel from the extruder is fed to the inlet end of the mixer and discharged from the outlet end, with flow in the y-axis direction.

From the mixer, the gel passes through a condenser as described in U.S. Pat. No. 2,669.751, and from the condenser it is passed to a die where it is extruded into rectangular plates. t
A similar extrusion device and a preferred extrusion device are shown in US Pat. No. 3,966.381.

In producing the foams of the present invention, it is often desirable to add a nucleating agent to reduce cell size. Talc, calcium silicate and indigo are suitable nucleating agents for cell size reduction. Various other additives may also be used, such as flame retardants and stabilizers.

A ci, 4 cTn (z34 inch) extruder is used in which the blowing agent is mixed with the molten resin, the resin is sent to a static cooler, cooled to the foaming temperature, and
3 inches) wide slot die. The resulting foam plank is approximately 2.5 x 20.3 cIn (
It had cross-sectional dimensions of 1 inch x 8 inches). If flame retardants, stabilizers and/or nucleating agents were added, these were dry mixed with the resin pellets before entering the extruder. The results obtained are shown in the table below. The following abbreviations were used in this table:

wt% Weight percent P P H Parts per 100 parts of resin FRA Hair retardant MGO Magnesium oxide DAP Sodium hydrogen phosphate Ba1t Barium stearate TF Foaming temperature, i.e. the temperature of the resin adjacent to the die slot before pressure is released ('C ) pcf bond/cubic feet u mm ■ Vertical or Thickness E Extrusion Direction ■ Horizontal or Width MeCL Methyl Chloride F-12 Dichlorodifluoromethane IPA Isopropyl Alcohol EtOH Ethyl Alcohol F-22 Chlorodifluoromethane Me OH Methyl Alcohol Board Molding Characteristics Pocket when removed from the molded plate assembly; Excellent... Relatively smooth skin with no rough surfaces; Good...
Has a slightly rough surface but can withstand most uses; OK...
- Too coarse for many uses.

Table (continued) 11 23 gtOH/23 F-22/-12,0-
-54F-12 1226EtOH/30 F-22/-13,5--4
4F-12 1350F-22150F-1212,0--1423
EtOH/23 F-22/-13,4FR-65IP
1.854 F-12 1523EtOH/23 F-22/-13,3FR-
651P 1.84F-12 1623EtOH/23 F-22/-13,0FR-
651P 1.854 F-1,2 1723MeOH/23 F-22/ 12.5 HB
CD 1854 F-12 188EtOH/23 MeOH/-13,3HBCD
1854 F-12/15 F-22 1923EtOH/23 F-22/-], 4.0 H
BCD 1.84F-12 −-0,075-128 −-0,075--117 −-0,075-131 −0,50,07--11,9 −0,50,070,01116 −0, 80,0750,1" -118 Next -0,250,150,10,075118 Next -0,20,150,10,1118 Next -0,20,150,10,03123 (Peck) 1 5.24 32 .3 0,37 0.305 0.
139 0.1192 5, io 47.7 0,45
0.157 0.221 0.1893 4.55
39.0 0.51 0.10B 0.200 0.1
474 4.34 35.7 0.44 0.125
0.236 0.1425 4.72 28.5 (1
,540,1030,0810,05865,4532
,80,51,0,1180,],45 (1,108
75,3841,80,530,1390,2060,
1,5584,3437,10,550,079-0,
1430,11795,6234,71,010,13
50,1900,1611o5.00 30.9 1,
26 0.128 0.121 0.114 Dimensional stability (%) -1,1-0,2-(1,3 + groan +1.49-0.58-0.06 good +1.67-0.86- 0.24 Good +1.52 -0.01 +0.67 Good +1.39-
0.35-0.14 Good-0, 13-0, 62-0, 28 Good +1.20 +0.5 Excellent → -1.4-0.1+0.6 Excellent (continued) 11 4.48 30. 1 0,78 0.096 0
．． 125 0.06612 5.1,7 34.4 1
,16 0.160 0.126 0.1521.3
5.79 35.0 0.41 0.19B 0.19
0 0.19114 5.51 32.8 0,25
0.216 0.139 0.13215 483 3
4.1 019 0.337 0.121 0.127
16 3.8fi 32.3 0.28 0.255
0.078 0.10817 4.34 33.8 0
．． 68 0.196 0.14.5 0.15418
3.96 36.3 0.65 0.206 0.17
9 0.1.6019 4.65 28.3 f), 4
8 0.210 0.066 0.081 Dimensional stability (
h) +1. ．． 7 -0.3 +1. O vague +0.5 +1.0 +0.6 1 love +0.7 +0.5 +0.6 good +0.4 +0.3 +O,7 good 0 +1.2 +1. ．． 1 Excellent + 1.5 + 2.0 + 0.1 Excellent + 0.3 + 0.2 - 0.2 Excellent + 0.1 -0.2 -1.1 Excellent + 1.7 + 1.7 + 0.5 Closed Table (Continued) Note : Samples m3 to 16 are 9% isopropanol, 4.3%
Samples N1118 and 1
No. 9 was produced using 11.7 timethanol and ethanol denatured with o, s M113.

A phthalocyanine blue pigment was used instead of indigo.

The US federal standard for DAP-diammonium hydrogen phosphate shaft insulation products is 70°C (158'F).
)/95% relative humidity for 7 days of exposure, all dimensional changes within +2.0% in any direction are required.

One day after production, 22 hours at 75°C (below 167°C).

Table (continued) 20 23 EtOII/23 F-227-12,0
FB-65IP 1.054 F'-12 2123EtOH/23 F-227-12,0FR-
65IP 1.054 F-12 22231 (tOH/23 F-227-12,0HB
CD 1. Q4F-12 2323EtOH/23 F-22/-12,0HBC
D 1.054 F-12 2423) C1OH/23 F-22/-12,0HB
CD 1.054 F-12 (+, (+3 - 0.07 0.01 125- 0
．． 25 0.07 0.01 123- 0.25 0
,07 0.01 1280.05 - 0.07 0
．． 01 128- 0.25 0.0? 0.01 1
Table 25 (continued) 20 33.0 0.30 +0.09 -0.91
-0.17 Excellent 21 31.5 0.32 -0.74
-0.53 -0.88 Excellent 2230.70.75
+1.54-0.64-0.97 Excellent 2330.70.5
8 +0.46-0.74-0.60 Excellent 2432.00
．． 61 +0.75-0.52-0.96 Excellent Note: *Rome Blue Ephthalocyanine Blue Pigment Die Pressure = 4.1
．． 4-4.83 MPa Sample - Prepared using ethanol denatured with 20-24.7% mechnol and 08% MIBK.

Conventional dimensional stability standards require a dimensional change of less than 2% in any direction.

Due to the presence of chlorofluoromethane, all bodies according to the invention exhibit excellent thermal preservation over time and provide excellent dimensional stability as measured by heating the bodies at 75° C. for 22 hours.

Patent Applicant: The Dow Chemical Company Continued from Page 1 [Phase] Inventor: Burke Nidward, Amedienner, United States of America, Ohio 43062 Kalanti Obking Peter Scala E Oak Meadow Dob 1O8 Procedural Amendment (Method) February 10, 1980 Patent Office Director Kazuo Wakasugi (1988) Patent No. 239037 (1982) Name of the invention Method for producing styrene polymer foam and foam produced thereby3 Relation to the M sound-stopping case Patent applicant Name: The Tau Chemical Company Name: Patent Attorney (6323) Ryoji Yose/'11:1\1 ・,・1 5, 7J Elephant of Correction (,,:I &11 V?-Saturated Hands) Specification .

There is no inherent correction.

Claims (1)

[Claims] 1. Heat-plasticizing an alkenyl aromatic synthetic resin material, adding a volatile fluid blowing agent to the heat-plasticized synthetic resin material,
The fluid blowing agent is mixed with a plasticizing resin to form a foamable resin mixture, the temperature of the mixture is reduced to a temperature such that a foam is obtained when pressure is removed therefrom, and the pressure on the mixture is The mixture is formed into a foam by reducing the mechanical and transverse directions of an elongated foam of a qualified alkenyl aromatic thermoplastic resin formed within a large number of closed, non-interconnected, gas-containing cell tubes. In a method for producing; (1) about 5 to 20% by weight of isopropyl alcohol, 5 to 50% by weight of chlorodifluoromethane, and 3
A mixture with 0-70% by weight of dichlorodifluoromethane;
■ A mixture of 5 to 50% by weight of ethanol, methanol or a mixture thereof, 5 to 50% by weight of chlorodifluoromethane and 30 to 70% by weight of dichlorodifluoromethane; and mixtures thereof; An improved method characterized by the use of a defrosted blowing agent. 2. The blowing agent is 5-20% by weight of isopropyl alcohol, 5-50% by weight of chlorodifluoromethane, and 30-70% by weight of isopropyl alcohol.
2. A method according to claim 1, wherein the mixture is a mixture of dichlorodifluoromethane. 3. The method according to claim 1, wherein the blowing agent is a mixture of 5 to 50% by weight of ethanol, 5 to 50% by weight of chlorodifluoromethane, and 30 to 70% by weight of difluoronocone. . 4. The method according to item 1, wherein the blowing agent is a mixture of 5 to 51% by weight of methanol, 5 to 50% by weight of cyclodifluoromethane, and 30 to 70% by weight of cyclodifluoromethane. 5. The method according to claim 1, wherein the alkenyl aromatic thermoplastic resin is styrene. 6. Heat plasticizing an alkenyl aromatic synthetic resin material, applying a volatile fluid blowing agent to the heat plasticized synthetic resin material, and mixing the fluid blowing agent with the plasticized resin to form a foamable resin mixture; By actually lowering the temperature If of this mixture such that when the pressure is removed therefrom it changes to an emitted form, and by reducing the pressure of the mixture to make it an emitted form, and (1 ) 5-20% by weight of isopropyl alcohol and 5-20% by weight of isopropyl alcohol
Mixture of 50% by weight chlorofluorocane and 30-70% by weight dichlorodifluoromethane; (2) 5-50
a mixture of 5% to 50% by weight of chlorofluorocarne and 30 to 70% by weight of dichlorodifluoromethane; and mixtures thereof; An elongated foam of an alkenyl aromatic thermoplastic resin having a mechanical direction and a transverse direction and having a large number of closed, non-interconnected gas-containing cells formed therein produced by an extrusion method using a milling process. , these Sergalo 1 to 1.2, preferably 01 to 0
．． With an average cell size of 9.9 mm, the emitter consists of a uniform cell structure with no discontinuities, and is determined by the average cell diameter across the smallest cross-sectional dimension of the emitter (i.e., according to ASTM method D2842-69, for example). ) the emitters have no practical variation in average cell size when the cell dimensions are measured, and the elongated emitters have a +9i surface dimension of at least 51.6- and a minimum cross-sectional dimension of at least 0.64 cm; ASTM method C355-64 where the emitter is desiccant method
The cell has a water vapor transmission rate of less than 30 paml as measured by the procedure of The permeability of nitrogen through the body is 1,017 times lower than that of iTgll and 12 Cl.
-Contains C3 monohydric alcohol, and has 012
It has a thermal conductivity of / m / °C,
Synthesis 4☆1 lipothermal nJ plasticity/l” 2 bodies.