JPS6028853B2 - Foaming compositions and their uses - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to thermoplastic blends of thermoplastic organic polymers and dihydrooxadiazinone.

More particularly, the present invention relates to foamable compositions, thermoplastic foams, etc.
and foam structures made from the composition. Prior to the present invention, the plastics industry had devoted considerable research and development into high performance thermoplastic platforms for the purpose of manufacturing lightweight structures as replacements for metals in various applications such as those used in the automotive industry. effort was expended.

As shown in U.S. Pat. No. 3,888,801, hydra is commonly used as a blowing agent in various thermoplastic organic polymers for the purpose of reducing the overall weight of certain thermoplastic materials when molded into certain shapes. Zodicarboxylate has been used. Other blowing agents commonly used in various thermoplastic organic polymers include Muller et al., U.S. Pat.
No. 81233 and U.S. Pat. No. 3,779,954 to WMh et al.
5-phenyltetrazole, as shown in No.
benzamide etc. hydrazodicarboxylate such as diisopropyl hydrazodicarboxylate and 5
- Phenyltetrazole has been found to be effective in reducing the density of various thermoplastic organic polymers, such as polycarbonate, polyester, polyacrylate, etc., but deterioration of the polymer during the foaming process is not negligible. It has been shown that there are some problems. Polymer degradation is generally indicated by a decrease in the polymer's intrinsic viscosity when comparing the polymer's intrinsic viscosity before and after foaming. Polymer degradation is directly related to a reduction in the impact strength of the platform. Although not completely understood, this is one possible explanation as to why blowing agents such as the hydrazodicarboxylates mentioned above can cause a significant degree of polymer degradation during foaming. If the blowing agent contains decomposition by-products such as aliphatic alcohols,
It is conceivable that it may contain chlorine, ammonia, water, etc.

Blowing agents such as penzazimide and bisbenzazimide mentioned above also tend to degrade the polymer due to the production of water as a decomposition by-product. Those skilled in the art are aware of the need to carefully dry high performance thermoplastics, such as polycarbonate, before molding due to the risk of polymer degradation. Therefore, it can be used in a variety of high-performance thermoplastic organic polymers such as polyester, polycarbonate, etc., without deteriorating these thermoplastic polymers, and which is normally expected since the change in density of the material occurs as a result of foaming. It would be desirable to provide a blowing agent that is more resistant to adversely reducing the impact strength of home products. The present invention is based on the following findings.

That is, for example, M. Rosenblum et al. , J.
．． Amer. Chem. Soc, 85, 3874 (1
963) 170oo to 31 as indicated by
Dihydroxanediazinone, which has the highest decomposition rate in the temperature range of 1,000,000, can be used in various organic thermoplastic polymers such as polycarbonates, polyesters and other polymers as defined in more detail below to yield formulations. The formulation can be injection molded into various foamed shapes without appreciable changes in the intrinsic viscosity of the organic polymer or with any more than would normally be expected reductions in the impact strength of the foamed structure. The present invention provides a substantially homogeneous, injection moldable composition comprising a thermoplastic polymeric material and a dihydrooxadiazinone blowing agent in a proportion of 0.1 to 25% of the composition; The material can be converted into a substantially homogeneous thermoplastic home by conventional injection molding conditions or used as a concentrate to produce an injection moldable composition convertible into a home.

Dihydrooxadiazinones that can be used to prepare the formulations of the present invention include compounds having the formula:

In the above formula, a is an integer of 1 or 2, and R is a monovalent group when a is 1 and a divalent group when a is 2.
an alkyl group or alkylene group, a C(6-3o) aryl group or arylene group, and halogenated derivatives thereof. RI and R2 are the same or different monovalent groups selected from hydrogen, C(,~8)alkyl, alkylene, C(6~3o)aryl, arylene, alkoxy, and aryloxy, and RI and R2 are When both are alkyl, RI and R2 can form part of an alicyclic ring structure. The group encompassed by R in formula 1 is C(,
~8) Alkyl groups such as methyl, ethyl, propyl, butyl, etc., aryl groups such as phenyl, tolyl, xylyl, naphthyl, anthryl, etc., haloalkyl such as chloroethyl, trifluoropropyl, etc., haloaryl such as chlorophenyl, furomotryl, etc., nitroaryl and sulfoaryl It is.

The groups encompassed by RI and R2 are hydrogen and C(,
~8) Alkyl groups such as methyl, ethyl, propyl, etc.
Alkoxy groups such as methoxy, ethoxy, bropoxy,
butoxy, aryloxy groups such as phenoxy, cresoxy, naphthoxy, etc. Particularly when RI and R2 are both alkyl, RI and R2 are cyclobentyl, cyclohexyl, cyclo. It can form part of an alicyclic ring structure such as heptyl. Otherwise, RI and R
2 are both aryl, then these are RI and R2
may be phenyl, tolyl, xylyl, naphthyl, anthryl or a mixture of any two of the above aryl groups. Some examples of dihydroxadiazinones that can be used in the practice of this invention include 5,6-dimethyl-3,6
-dihydro 1,3,4-oxadiazin-2-one,
5,6,6-trimethyl-3,6-dihydro-1,3.
4-Oxadiazin-2-one, 5-ethyl-6-methoxy-3,6-dihydro 1,3,4-oxadiazin-2-one, 5,6-diphenyl-3,6-dihydro-
1,3,4-oxadiazin-2-one, 5-(p-furomophenyl)-3,6-dihydro 1,3,4-oxadiazin-2-one, 5-phenyl-6-methyl-3
・6-dihydro-1.314-oxadiazin-2-one, 5.6-bis(p-methoxyphenyl)-3.6-
Dihydro-1,3,4-oxadiazin-2-one, 5
-Naphthyl-3,6-dihydro 1,3,4-oxadiazin-2-one, 5-(o.o.p-tribromophenyl)-6-propyl-3,6-dihydro 1,3,4
-Oxadiazin-2-one, 5-(p-hydroxyphenyl)-3,6-dihydro1,3,4-oxadiazin-2-one, 5-phenyl-6,6-cyclobenzene-3,6-dihydro1,3. 4-Oxadiazin-2-one, 5-(m-nitrophenyl)-3,6-dihydro 1,3,4-oxadiazin-2-one, 5-
(p-benzenesulfonic acid sodium salt)-3,6-dihydro-1,3,4-oxadiazin-2-one, 5-
(2-fluorenyl)-6-trifluoroethyl-3.
6-dihydro-1,3,4-oxadiazin-2-one, 5-phenyl-6-(cyanophenylmethyl)-3.
6-dihydro-1,3,4-oxadiazin-2-one, 5-phenyl-6-cyano-6-methyl-3,6-dihydro-1,3,4-oxadiazin-2-one and 2
Some have polycyclic formulas, such as those resulting from valence substitution.

The term "thermoplastic polymeric material" is e.g.
Includes any organic polymer that can be injection molded at least twice at a temperature in the range of 000 to 000, such as polycarbonates,
Polyesters, such as polybutylene terephthalate, polyethylene terephthalate, polybutylene-terephthalate-polybutylene oxide copolymer, poly(4
・4-cyclohexylidene diphenylene isophthalate), poly(4,4-isopropylidene diphenylene isophthalate), poly(p-hydroxybenzoic acid), polyolefins such as poly(hexafluoropropylene)
, polypropylene, polyacrylates and polymethacrylates, polystyrenes such as polystyrene, poly(
Poly(4-t-butylstyrene), poly(4-furomostyrene), poly(Q-methyl-styrene), polyamides such as polycaprolactam and polyhexamethylene adipamide, polyvinyl chloride, polyphenylene oxide matrix resins (blends with polystyrene) ), polyarylsulfones, A-spotted polymers, polystyrene acrylonitrile copolymers, polyacetals, urethane elastomers, polyphenylene sulfides, polyimides, polysilphenylenes, and the above components copolymers, flock copolymers, polymer blends, and alloys.

In the practice of the present invention, thermoplastic compositions can be prepared in dry powder form, extruded pelletized form, extruded thermoplastic sheet form, etc., depending on the melting characteristics of the thermoplastic polymeric material and the decomposition temperature of the blowing agent. .

The decomposition temperature of the blowing agent (hereinafter used interchangeably with the term "dihydrooxadiazinone" as defined above) is below, near, or above the temperature at which the thermoplastic polymeric material can be melt extruded. In slightly higher cases, it is preferred to produce the thermoplastic composition in the form of a dry powder. The blowing agent exhibiting a maximum decomposition rate at a temperature of at least 2500 degrees above the melt extrusion temperature of the thermoplastic polymeric material comprised about 1 to 25% by weight or more of the blowing agent, based on the weight of the blowing agent and the thermoplastic polymeric material. An extrudable foamable composition or concentrate can be provided and further melt extruded with additional thermoplastic polymeric material to form a foamable composition. Approximately 0.1-1. Melt extruded pellets or sheets containing 50% by weight of dihydroxadiazinone can be converted into home structures at higher injection molding temperatures. The decomposition temperature of the blowing agent used to produce the foamable thermoplastic formulation in the practice of this invention is between about 170 CO and 310 QO
It is preferable to have the highest decomposition rate in the range of . A particularly preferred blowing agent-thermoplastic polymeric material combination in the form of either a concentrate or a foamable formulation is Gener
alElectric Company's trademark LEXAN
Polycarbonate resin commercially called polycarbonate resin and 5-phenol-3/6 as a blowing agent
-dihydro 1,3,4-oxadiazin-2-one. A preferred group of thermoplastic organic formulations that can be converted into high performance homes in accordance with the practice of this invention fall within the scope of the dihydrooxadiazinones previously defined as high performance thermoplastic organic polymers, where R3 is It is used in combination with dihydroxadiazinone represented by a monovalent or divalent C(6-3o) aryl group).

Preferred formulations can take the form of powder pellets or sheets, and the organic polymers include polycarbonate, polyphenylene oxide, polyphenylene oxide polystyrene blends, polyarylsulfones, polyimides and
- Selected from polycarbonate polymers produced by phosgenation or transesterification of 1-dichloro-212-bis(4-hydroxyphenyl)ethylene, polyesters derived from such dihydric phenols, polyamides, etc. The above thermoplastic organic polymers based on the use of 1,1-dichloro-2,2-bis(4-hydroxyphenyl)ethylene allow the production of high performance thermoplastic platforms.

An example of the use of such chloral-derived dihydric phenols is
Kai iew Dobko ship kietal. , Synthes
isof Polycarbona by lnt
eMaciaI Me ratio od, Pol's meri -
TworZyWa Wielkocas cZkow
e (1970). Another preferred foamable thermoplastic formulation that can be used in the practice of this invention is represented by M. Rosenblum et al.
, Chemist and Industry, Pa bag 1
480 (King December 15, 1953) using 3,6-dihydro-516-diphenyl-1,3,4-oxadiazin-2-one.

The diphenyl-substituted dihydroxadiazinones are preferably melt-extruded in combination with any one or more of the aforementioned thermoplastic organic polymers having desirable melt properties, particularly polyalkylene terephthalate esters such as polybutylene terephthalate esters. or in the form of melt extruded thermoplastic sheets.

The thermoplastic formulations of the invention may also contain other active or inert fillers such as carbon black, glass fibers, stone powder,
antioxidants, stabilizers such as lead, cadmium, calcium, zinc, tin or barium salts, waxes, dyes, pigments,
It can contain zinc oxide and the like.

In addition to the above thermoplastic formulations in beret, powder or sheet form, the present invention also relates to foamed shaped structures derived from the above formulations, such as by conventional injection molding techniques, The structure has improved impact strength.

The following examples are provided to enable those skilled in the art to better practice the invention.

However, the examples are for illustrative purposes only and are not meant to be limiting. All parts are by weight. Example 1 Preparation of dihydroxadiazinone and specifically 5-phenyl-3,6-dihydro-1,3,4-oxadiazin-2-one used as blowing agent in the preparation of the thermoplastic formulations described below. was done as follows.

About 13 parts of bromine was slowly added to a mixture of 474.6 parts of acetophenone in about 64 parts of methanol while the mixture was maintained at a temperature of 5-100°C.

Hydrogen bromide gas was introduced into the mixture until the bromine color disappeared, at which point additional amounts of bromine were added over 2 hours for a total of 631.3 parts. 71 parts of water were then added while the mixture was allowed to cool externally for about 30 minutes. Approximately 270 parts of excess water was then slowly added to precipitate Q-bromoacetophenone from the mixture in crystalline form. The crystals were decanted by vacuum siphon, washed and neutralized with 20% sodium hydroxide solution, then decanted and dried. A sodium formate solution prepared from approximately 940 parts water, 1600 parts methanol, 333 parts sodium bicarbonate, and 161 parts 90% formic acid and enough sodium hydroxide to neutralize the acid was then added. The mixture was heated to 6000 °C for 7 hours with vigorous heating, then cooled to ambient temperature and filtered. Based on the method of preparation and gas chromatographic analysis of the mixture, Q-hydroxyacetophenone was produced in quantitative yield. Dilute hydrochloric acid was added to the above furnace liquor mixture along with 855.8 parts of methyl carbazate prepared from equivalent amounts of hydrazine and dimethyl carbonate.

The amount of hydrochloric acid used was sufficient to bring the pH to 5.5, after which the mixture was heated at 380 for 6 hours. A crystalline precipitate formed which was filtered from the mixture and washed with water. Based on the method of preparation and spectroscopic analysis, the product is Q
-Carbomethoxyhydrazone of hydroxyacetophenone. The above carbomethoxyhydrazone and about 190
The mixture of anchorage and toluene was refluxed under reduced pressure to remove residual water from the crystalline product.

Anhydrous potassium carbonate was then added to the mixture and heating was continued under reduced pressure to remove any tano-toluene azeotrope. Next, the mixture was allowed to cool and the above-mentioned blowing agent 5-phenyl-3,6-dihydro 1,3,4-oxadiazine-2 was added.
-on, which was finally dried in a vacuum oven at 70-80 qo. The overall yield of final product was 456 parts, which is a 65.5% yield based on acetophenone. The melting point of this product was 163-165q○. Average intrinsic viscosity of 2500 in chloroform is approximately 0
．． Bisphenol-A with a density of about 1.17 at 55%/day
A dry powder blend of polycarbonate resin powder and the above-described blowing agents of the present invention and the commercially available blowing agent isopropyl hydrazodicarboxylate was prepared such that each blowing agent comprised 0.6 parts per 10 parts of polycarbonate resin. It was prepared as follows.

The polycarbonate was in the form of a finely divided powder that was dried for 1 hour at 125 qo. The formulation is approximately 28〆0
Melt extrusion was carried out at temperatures ranging from 0 to 305 pm. A thermoplastic home was formed from the finely divided dry blend during melt extrusion. In addition to melt extruding the foamable formulation described above, the same polycarbonate resin without blowing agent was also melt extruded. The density (in/cc) of each blended and unblended resin was determined from samples extruded over a temperature range of 28°C to 305°C. The intrinsic viscosity of the polycarbonate resin and the intrinsic viscosity of the polycarbonate resin and the above formulation in chloroform at 2500 °C is also 2.
Molecular weight loss, if any, due to polymer degradation during the foaming process was also determined from samples extruded over a temperature range of 8.0 to 32.0. The table below shows the results obtained, where T is in °C, density indicates the change that occurred over temperature as a result of foaming, and IV indicates the degradation of the polymer due to blowing agent by-products. The results show any changes, if any, in the intrinsic viscosity of the polycarbonate resin, with formulation A containing dihydroxadiazinone according to the invention and formulation B containing isopropyl hydrazodicarpoxylate. are doing. The above results indicate that the molding temperature of Formulation A of dihydroxadiazinone of the present invention is somewhat higher than that of Formulation B of isopropyl hydrazodicarboxylate.

More noteworthy, however, is that the blowing agents of the present invention have been shown to cause no appreciable changes in the intrinsic viscosity of the polycarbonate as a result of the blowing action. Polymers extruded using prior art isopropyl hydrazodicarboxylate blowing agents showed a 15% decrease in polymer intrinsic viscosity, indicating significant polymer degradation. ing. Example 2 Various thermoplastic foamable formulations were dry blended on polycarbonate pellets containing 5% glass fiber.

The density of the polycarbonate resin used to make the glass-filled pellets was approximately 1.2 Ta'cc. These various formulations contain approximately 0.25 blowing agent per 10 parts of pellet.
The blowing agent of the present invention, dihydroxadiazinone, as shown in Example 1, and the conventional blowing agent discussed in Example 1, including 5-phenyl-tetrazole, another conventional blowing agent. It was. SiemagStr various formulations
...I converted it into a 12x/2x cubic inch panel using a tomat home injection molding machine. The impact strength of the panel was measured by the bell spear drop method (ASTMD1709-62r), and
All panel density measurements obtained were 0.85 ta'cc.
was. The table below shows the impact results obtained from various panels. Example 3 The various polycarbonate resin formulations of Example 2 were first made into pellets and then injection molded into test beams to measure Izod impact strength (ASTM D-256-56).

In order to make test bars from this 5-phenyltetrazole formulation, it was necessary to injection mold the thermoplastic formulation in the form of a beretto powder mixture. The table then shows the results obtained regarding the comparison of the changes occurring in the intrinsic viscosity when changing from pellet to bar and the changes in the unnotched Izod impact results, where IV is as previously defined. be. The results in the table show that the use of different blowing agents resulted in significant changes in the intrinsic viscosity of the foam panel bars.

When using isopropyl hydrazodicarboxylate compared to the dihydroxadiazinone of the present invention,
The change that occurred in the intrinsic viscosity of the polycarbonate also changed the unnotched Izod impact value. Although 5-phenyltetrazole did not degrade polycarbonate as severely as isopropyl hydrazodicarboxylate,
-Phenyl-tetrazole does not have a sufficiently high decomposition temperature to convert into pellet form prior to conversion into test panels, so its use has been limited to the form of a dry powder formulation.

This clearly shows that the dihydroxadiazinone blowing agents of the present invention offer significant advantages in flexibility, molding process and providing thermoplastic home products with superior impact strength. There is. Example 4 10 anchors of polycarbonate resin containing 5 parts of the dihydroxadiazinone blowing agent of Example 1 and 10 anchors of polycarbonate resin.

Each extrusion concentrate in pelletized form containing 5 parts of lopyl hydrazodicarboxylate was mixed with 5% glass fiber-containing polycarbonate resin at a rate of $1 per part of pelletized concentrate. . These foamable formulations were then home molded in a Sjemag Structomat home injection molding machine to yield panels measuring 2 x 2 x cubic inches.

The density of the panel was 0.85 m/cc. The impact strength of the panel was measured by the bell and spear drop method (ASTMD/1709/62T). Impact strength of panels obtained from concentrate containing dihydroxadiazinone blowing agent was 9 mt·lb on average.
It was s. The impact strength of the panels provided by the concentrate obtained from the isopropyl hydrazodicarboxylate blowing agent averaged only 6 t·lbs. Example
Polyester (trade name VALOX310) manufactured by 5General Electric Company
) 23,500 to 23,500 to 23,500 parts of tumble-blended mixed formulation C comprising 0.6 parts of 5,6-dipheny-3,6-dihydro-1,3,4-oxadiazin-2-one per 100 parts.
Extruded over a temperature range of 25,400°C.

The intrinsic viscosity IV of the foamed polyester resin extrudate was measured in heptafluoroisoprobenol at 25°C to determine the degree of molecular weight reduction, if any, due to polymer degradation during the foaming process. Comparison was made with unfoamed extruded polyester. The densities of these extruded samples were measured in the same manner. The table below shows the results obtained. Judging from the above results, dihydrooxadiazinone reduces the density extremely well, and what is more noteworthy is that the foaming agent of the present invention also has a foaming effect that is unique to polyester resins. It does not reduce the viscosity appreciably and therefore shows little or no deterioration of the polyester.

Example 6 A formulation was prepared using 15 parts of 5,6-diphenyl-3,6-dihydro-1,3,4-oxadiazin-2-one and 85 parts of Hytre 14056, a polyester-polyether copolymer. Prepare and die temperature 2000
Br under the conditions of 0, central castle 139qo, rear castle 188℃
It was extruded into pellets using an abender device.

The extrudate showed no signs of foaming. The above polyester-polyether copolymer containing 15% dihydroxadiazinone was used as a blowing agent concentrate for foaming polyesters such as poly(butylene terephthalate), and 3 parts of polyester resin was foamed. agent concentrate 1
The mixture thus obtained was heated to a temperature of 24°C.
3qo, center 254oo, front 240qo, type 93qo
Foam molding was carried out under the following conditions. A 35% decrease in density of the molded part was observed. Example 7 5-Phenyl-3,6-dihydro-
A tumble-blended mixture containing 0.7 parts of 1,3,4-oxadiazin-2-one was added to the Ba ratio KM70.
/10 Ship injection molding machine with rear temperature 299 0, center 3
02℃・31o in front.

It was foam-molded into a flat plate with dimensions of 3 x 3 inches x 1 inch under O-shaped chest conditions. The density of the foamed plate was 0.51 T/cc, and the density of the same plate without foaming agent was 1.27 T/cc. Example 8 A tumble-blended mixture containing 0.7 parts of 5-phenyl-3,6-dihydro-1,3,4-oxadiazin-2-one per 100 parts of acrylonitrile-butadiene-styrene (ABS) copolymer was A flat plate was formed into a foam board shape in the same manner as in Example 7 under the conditions of temperature 260°C, center 29000°C, front 288°C, and mold 38°C.

The density of the foamed flat plate is 0.61/cc, and the density of the same flat plate without foaming agent is 0.999/cc.
It was c. Example 9 1 part of 5-phenyl-3,6-dihydro per 10 parts of polymer alloy of polyphenylene oxide and polystyrene
A rolling blend mixture containing 0.7 parts of 13,4-oxadiazine-2-one was heated at a rear temperature of 293°C, a center of 299qo,
It was foam-molded into a flat plate in the same manner as in Example 7 under the conditions of 304 qo for the front and 49 qC for the mold.

The density of the foamed plate was 0.5cc, and the density of the same plate without foaming agent was 1.07cc. Example 10 Hexamethylene diamine-adipic acid polyamide resin 1
A rolling mixture consisting of 0.5 parts of 5,6-diphenyl-3,6-dihydro 1,314-oxadiazin-2-one per 0 anchor was heated at a rear temperature of 238°C and a center of 249qo.
, the front part 25 was foam-molded as in Example 7 under the conditions of 0.0 and mold 5.0.

The density of the foamed flat plate is 0.53 mm/cc, and the density of the same flat plate without the foaming agent is 1.01 mm/cc.
was. Example 11 Polypropylene 5 per 10 anchors
・A rolling mixture consisting of 0.7 parts of 6-diphenyl-3,6-dihydro-1,3,4-oxadiazin-2-one was heated at a temperature of 180°C at the rear, 220°C in the center, and 230°C in the front.
o. Foam molding was carried out as in Example 7 under conditions of mold temperature 25°C.

The density of the foamed flat plate is in the range of 0.5 to 0.7 T'cc, and the density of the same flat plate without foaming agent is 0.9.
It was 5 evenings/cc. Example 12 5,6-diphenyl-3,6-dihydro-1,3,4-oxadiazine-2 to 100 parts of high impact polystyrene
- A rolling blend mixture consisting of 0.7 parts of
000, center 2490C, front 26000, type 38oo
Foam molding was carried out as in Example 7 under the following conditions.

The density of the foamed flat plate was 0.68 m/cc, and the density of the same flat plate without the foaming agent was 1.04 m/cc. Example 13 Isotactic polystyrene 1 with a molecular weight of 200,000
A slurry was prepared by adding one anchor of 5-phenyl-3,6-dihydro-1,3,4-oxadiazin-2-one to a solution consisting of an anchor and eight anchors of methylene chloride.

This slurry was rapidly mixed and then fed to the spray dryer nozzle. The slurry was injected into a chamber and air heated to 70 qo was circulated through the chamber. 100
Collect granules with mesh sizes ranging from ~200 to 50
It was dried in a vacuum oven at midnight.

The thus obtained granules contain dihydrooxadiazinone encapsulated in polystyrene and consist of about 1 part of dihydrooxadiazinone per 1 part of polystyrene. One part of this encapsulated blowing agent was tumble blended with 9$ of bisphenol-A polycarbonate resin, and then the back temperature was 54,000, the center was 575, and the front was 500℃.
Foam molding was carried out as in Example 7 under the conditions of 70 qo and mold temperature of 95°C.

The density of the thus foamed flat plate was 0.85 T'cc, and the density of the unfoamed flat plate was 1.19 T'cc.
Example 14 A rolling blend mixture consisting of 0.7 parts of 5,6-diphenyl-3,6-dihydro 1,3,4-oxadiazin-2-one per 10 parts of polyester-polyether copolymer Hytrel 4056 was added to the rear. Temperature 22600, center 23800, front 249℃, mold 25
It was foam-molded into a flat plate as in Example 7 under o0 conditions.

The density of the foamed flat plate was 0.68 T'cc, and the density of the same flat plate without the foaming agent was 1.13 T/cc. Example 15 S. Porejko and Z. “Syn” by Wielgosz
thesis andProperties of P
olyCarbona Company S Witn ChioroB
isphenols”, Polyme Hi13, ■55,
(1968) based on dehydrochlorination of 1,1-dichloro-
Synthesis of 2,2-bis(4-hydroxyphenyl)ethylene.

1,1-dichloro2,2-bis(4-hydroxyphenyl)ethylene 26.25 parts, sodium gluconate 0
．． 026 parts, phenol 0.237 parts, triethylamine 0.142 parts, methylene chloride 123 parts, and water 75 parts
The mixture consisting of 50% of the total amount was stirred at about 28 qo for about 10 minutes.

This mixture is then adjusted to a pH of approximately 1 in the aqueous phase of the mixture.
An amount of aqueous sodium hydroxide solution was added to adjust the amount to zero. While stirring the mixture, phosgene was introduced at a rate of about 12.24 parts per hour while sufficient 20% aqueous sodium hydroxide solution was added to maintain the pH of the aqueous phase of the mixture at 10.

Phosgenation of the mixture continued under these conditions for about 45 minutes, after which time the rate of phosgenation was reduced to about 6.8 parts per hour while maintaining the pH of the aqueous phase in the range of about 11-11.5. Phosgenation of the mixture was continued for about an additional 50 minutes. The reaction mixture was then diluted with about 10 parts methylene chloride and washed alternately with dilute hydrochloric acid, dilute sodium hydroxide, and water.

The mixture was then centrifuged, filtered and steam precipitated. After collecting the precipitate and drying at 8000, 26 pounds of product was obtained. Based on the method of preparation, the product is 1,1-dichloro-2,2-bis(4
-hydroxyphenyl)ethylene polycarbonate. The above dichloroethylene polycarbonate is 5-
Phenyl-3,6-dihydro-1,3,4-oxadiazin-2-one and glass fiber were combined to produce a formulation having 0.5% by weight blowing agent and 5% by weight glass fiber.

The mixture was then melt extruded at 5000F into pellets. According to ASTM-E-162-67, the above compound was foam-molded from the above pellet at 5750F to obtain 6×.
An 8 x cubic inch test panel was prepared.

This material had a Gardner impact value of about 25-37.8 t·ld and a density of about 1.07. Equivalent test panels were also prepared from a formulation of dichloroethylene polycarbonate described above and 5% by weight of glass fibers without blowing agent. ASTM-E-16 using these test panels
The flame retardation properties of glass-filled dichloroethylene polycarbonate and rigid platforms made therefrom were evaluated in accordance with 2-67.

Test panels with and without foam had an ls value of 0, which is equivalent to asbestos. The ls measurement for the foamed panels was 0.8, indicating that foaming the original formulation of dichloroethylene polycarbonate glass fibers did not significantly reduce the flame retardation properties of the original formulation. There is. Example 16 Approximately equal weight parts of the dichloroethylene polycarbonate of Example 15 and bisphenol-A polycarbonate having an intrinsic viscosity of about 0.55 d'' in chloroform at 25 mm and 5% by weight of total glass fibers. and 0.5% by weight of the blowing agent of Example 15.

The blend was melt extruded at 5000F into pellets. Berets were also prepared from identical formulations without blowing agents. 600% of the formulation according to the method of Example 15.
Test panels measuring 6 x 8 square inches were prepared by foam molding at 0F.

The foamed formulation has an ls value of 3.9, which is approximately equal to the superior flame retardation value of the unfoamed formulation, 3.7. or,
The foamed formulation had an intrinsic viscosity of about 0.45/h at 2500 in chloroform, a Gardner impact value of greater than 5 sail·lb, and a density of about 1. Example 17 Dichloroethylene polycarbonate (from Example 15) 75
A blend of 1.5% and 25 parts of Amo resin was pelleted at 5000F with 0.5% blowing agent (from Example 15) and 5% glass fiber by weight of the blend.

The ls values were compared for foamed and unfoamed test panels of 6 x 18 x table inches according to OASTM-E-162-67, where the formulation was foam molded at 5750F to make test panels. However, it is 12.0 for non-foamed panels and 12.0 for foamed panels. The song was shown.

Example 18 Dichloroethylene bisphenol 13.1 ATO and bisphenol-AIO. 65 parts of 1,1-dichloro-2,2-bis(4-hydroxyphenyl)ethylene and 2,2-pis(4-hydroxyphenyl)propane (bisphenol-A) according to the procedure of Example 15. A copolymer was prepared.

The above copolymer was mixed with 5-phenylene-3,6-dihydro-1
- Bulleted as in Example 15 with 3,4-oxadiazin-2-one and glass fibers.

The ls value of the non-foamed panel is 3.

It was found that the ls value of the panel foamed with No. 8 was 4.0.

As shown in Examples 15-18, homes derived from certain compositions of the invention give high ls values.

Such a home is a chemical bond of the formula (wherein R4 and R5 are the same or different divalent aromatic groups containing 6 to 13 carbon atoms, x is a halogen atom, and XI is X or hydrogen). At least 5 haloalkylene polycarbonate units
% by weight of a thermoplastic organic formulation.

The thermoplastic organic formulation can be reinforced with up to 6% by weight of glass fibers, and the formulation can be reinforced with haloalkylene polycarbonates, blends of such haloalkylene polycarbonates with other thermoplastic polymers as defined above, or as described above. It can also consist of a copolymer of haloalkylene carbonate units and other bisphenol carbonate units.
The present invention also provides a foamable composition which may be in the form of pellets or powder mixtures as previously described.
A method of producing foamed shapes by injection molding at a temperature of 0 qo is also provided. The term thermoplastic organic polymer as defined above includes polycarbonates having chemically defined units.

In the above formula, Z is selected from the group consisting of R6 and R6-Q-R6, and R6 is 2 having 6 to 1 needle carbon atoms.
Q is a divalent alicyclic group, oxyaryleneoxy group, sulfonyl, sulfinyl, oxy,
selected from the group consisting of thio, fluorenyl and phenolphthalein, and R7 is C(,~8)alkyl, R
6 and halogenated derivatives thereof.

Claims (1)

[Claims] 1 Thermoplastic polymer material and formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the above formula, a is an integer of 1 or 2, and R is a monovalent group when a is 1; When a is 2, C_(_1
The alkyl group or alkylene group of _～_8_) and C_(
selected from _6_ to _3_0_) aryl groups or arylene groups and halogenated derivatives thereof, and R^1 and R
^2 is the same or different monovalent group selected from hydrogen, C_(_1_~_8__) alkyl, alkylene, C_(_6_~_3_0_) aryl, arylene, alkoxy, and aryloxy, and R^1 and R When both ^2 are alkyl, these R^1 and R^2 can form a part of an alicyclic ring structure). and 0.1 to 25% by weight based on the thermoplastic polymer material)
An injection moldable, foamable composition containing. 2. The composition according to claim 1, comprising 0.1 to 1.0% by weight of dihydroxadiazinone. 3. A composition according to claim 1 or 2 which is a dry powder mixture of a finely divided resinous thermoplastic polymeric material and a dihydroxadiazinone blowing agent. 4 Dihydroxadiazinone is 5-phenyl-3.6
-dihydro-1,3,4-oxadiazin-2-one. 5 Dihydroxadiazinone is 3,6-dihydro-5
・6-diphenyl-1,3,4-oxadiazine-2-
The composition according to any one of claims 1 to 3, wherein the composition is on. 6. A composition according to any one of claims 1 to 5, wherein the thermoplastic polymeric material is a polycarbonate of 2,2-bis(4-hydroxyphenyl)-propane. 7. Any one of claims 1 to 5, wherein the thermoplastic polymer material is polyalkylene (terephthalate).
The composition described in Section. 8. A composition according to any one of claims 1 to 5, wherein the thermoplastic polymeric material is a polyphenylene oxide based resin. 9 The thermoplastic polymer material has the formula▲mathematical formula, chemical formula, table, etc.▼ (However, R^5 and R^6 are the same or different divalent aromatic groups having 6 to 13 carbon atoms, is a halogen atom,
The composition according to any one of claims 1 to 8, containing at least 5% by weight of chemically bonded haloethylene bisphenol carbonate units (X^1 is X or hydrogen). 10 The thermoplastic polymer material is 1,1-dichloro-2,2
The composition according to any one of claims 1 to 5, which is a polycarbonate consisting mainly of -bis(4-hydroxyphenyl)ethylene carbonate units. 11 The thermoplastic polymer material is 1,1-dichloro-2,2
- Any of claims 1 to 5, which is a copolymer mainly composed of bis(4-hydroxyphenyl) ethylene carbonate units and 2,2-bis(4-hydroxyphenyl) propane carbonate units. The composition according to item 1. 12 Claims 1 to 1 containing a glass fiber reinforcing agent
12. The composition according to any one of paragraphs 11 to 12. 13 Claims 1 to 1, wherein the thermoplastic polymeric material is a blend of an acrylonitrile-butadiene-styrene terpolymer and a polycarbonate composed of haloethylene bisphenol carbonate units as defined in Claim 9. The composition according to any one of Item 5. 14. The thermoplastic polymeric material of claims 1 to 5, wherein the thermoplastic polymeric material is a blend of isopropylidene-bisphenol polycarbonate and a polycarbonate consisting of haloethylene bisphenol carbonate units as defined in claim 9. The composition according to any one of the items. 15 Thermoplastic polymer materials and formulas▲Mathematical formulas, chemical formulas, tables, etc.▼ (In the above formula, a is an integer of 1 or 2, and R is a monovalent group when a is 1, and 2 when a is 2) C_(_1
The alkyl group or alkylene group of _～_8_) and C_(
selected from _6_ to _3_0_) aryl groups or arylene groups and halogenated derivatives thereof, and R^1 and R
^2 is the same or different monovalent group selected from hydrogen, C_(_1_~_8__) alkyl, alkylene, C_(_6_~_3_0_) aryl, arylene, alkoxy, and aryloxy, and R^1 and R When both ^2 are alkyl, these R^1 and R^2 can form a part of an alicyclic ring structure). and 0.1 to 25% by weight based on the thermoplastic polymer material)
An injection moldable, foamable composition in the form of pellets containing. 16 Formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the above formula, a is an integer of 1 or 2, and R is a monovalent group when a is 1, and a divalent group when a is 2, C_( ＿１
The alkyl group or alkylene group of _～_8_) and C_(
selected from _6_ to _3_0_) aryl groups or arylene groups and halogenated derivatives thereof, and R^1 and R
^2 is the same or different monovalent group selected from hydrogen, C_(_1_~_8__) alkyl, alkylene, C_(_6_~_3_0_) aryl, arylene, alkoxy, and aryloxy, and R^1 and R When ^2 are both alkyl, these R^1 and R^2 can form part of an alicyclic ring structure). however,
The blowing agent is 0.1 based on the blowing agent and the polymeric material.
An injection moldable and foamable composition in the form of pellets containing ~25% by weight). 17 Thermoplastic polymer materials and formulas ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (In the above formula, a is an integer of 1 or 2, and R is a monovalent group when a is 1 and 2 when a is 2) C_(_1
_～_8_) alkyl group or alkylene group and C_(
selected from _6_ to _3_0_) aryl groups or arylene groups and halogenated derivatives thereof, and R^1 and R
^2 is the same or different monovalent group selected from hydrogen, C_(_1_~_8__) alkyl, alkylene, C_(_6_~_3_0_) aryl, arylene, alkoxy, and aryloxy, and R^1 and R When both ^2 are alkyl, these R^1 and R^2 can form a part of an alicyclic ring structure). and 0.1 to 25% by weight based on said polymeric material) in the form of a sheet. 18 (1) Thermoplastic polymer materials and formulas ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (In the above formula, a is an integer of 1 or 2, R is a monovalent group when a is 1, and a is 2 When C_(_1
_～_8_) alkyl group or alkylene group and C_(
selected from _6_ to _3_0_) aryl groups or arylene groups and halogenated derivatives thereof, and R^1 and R
^2 is the same or different monovalent group selected from hydrogen, C_(_1_~_8__) alkyl, alkylene, C_(_6_~_3_0_) aryl, arylene, alkoxy, and aryloxy, and R^1 and R When both ^2 are alkyl, these R^1 and R^2 can form a part of an alicyclic ring structure). and (2) injection molding said mixture at a temperature of 170°C to 400°C. Method of manufacturing thermoplastic molded homes.