JPS6053066B2 - Flame-retardant reinforced copolyester molding resin composition with non-dripping properties - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention generally relates to reinforced flame retardant molding resin compositions.

More particularly, this invention relates to copolyester molding resin compositions modified with reinforced flame retardant polycarbodiimides.
Molding resins such as glass-reinforced polypropylene terephthalate and polybutylene terephthalate are flammable.

The presence of many important toughening agents, such as glass, accelerates rather than retards the burn rate of these molding resins. Although toughening agents have a direct effect on the desirable physico-mechanical properties of the molding resin, the flammability of the composition precludes many advantageous industrial applications. No. 3,751,396, filed by the applicant of the present invention, discloses that when polypropylene terephthalate and polybutylene terephthalate molding resins containing certain flame retardants according to the prior art are exposed to flame, combustion particles drip out. It states that there is a tendency.

To overcome this drawback, the length to diameter ratio is 50:
Supplemental reinforcing agents, such as asbestos with one or more of them, may need to be mixed in additionally. However, the use of asbestos is particularly undesirable due to the possibility of inhaling asbestos fibers, which is a health hazard. Further, U.S. Pat. No. 3,794,617 discloses diols, dicarboxylic acids and compounds of the formula: .

) has been published on a method for producing a flame-retardant polyester fiber-forming composition comprising a condensation product of diol bromides. However, it is not stated that this polyester composition for forming special fibers can be used as a molding resin. It is well known that carbodiimides react with polyesters.

(U.S. Patent Nos. 3,193,5n, 3,193,52
No. 8, No. 3,193,524 and No. 3,835,0
Please refer to No. 98. ) For example, U.S. Patent No. 3,193
, No. 5n provides a method for stabilizing polyester compounds against hydrolysis using highly substituted polycarbodiimides having a molecular weight of about 500 or more and having three or more carbodiimide groups in the polycarbodiimide molecule. . U.S. Patent Nos. 3,193,523 and 3,193
, 524, discloses the use of monocarbodiimides to stabilize polyesters. Additionally, U.S. Patent No. 3,835
, No. 098 discloses the reaction of medium molecular weight thermoplastic elastomeric copolyesters with small amounts of polycarbodiimides to produce compositions exhibiting properties similar to those exhibited by highly polymerized copolyesters. No. 588,982 filed by the inventor on March 17, 1979 (N.W. Soichimasu, F.M.
．． Berardinelli and R1 Edelman) describe a process for making thermoplastic polyesters modified with certain polycarbodiimides.

The improved thermoplastic polyesters have high melt strength and are suitable for extrusion applications. The process consists of reacting a thermoplastic saturated polyester in the molten state with at least one polycarbodiimide, the polycarbodiimide being (a) unsaturated or having one methyl substitution on each aromatic ring; and (b) have at least three carbodiimide units per polycarbodiimide molecule. The resulting polycarbodiimide-modified thermoplastic polyesters have high melt strength and intrinsic viscosity and a low number of carboxylic acid end groups.

Polyesters with improved melt strength have improved die expansion characteristics and are useful in extrusion applications such as blow molding. No. 616,348, filed on the same day by the inventor, N.W. Thomas,
F. M. Berardinelli and R. Edelman) has published a method for making polyalkylene terephthalate molding resin compositions improved with reinforced polycarbodiimides.

This method consists of intimately mixing the reinforcing agent with a polyalkylene terephthalate polymer, such as polybutylene terephthalate or polypropylene terephthalate, in the molten state; The method is to modify a polyalkylene terephthalate polymer by reacting it with a polycarbodiimide of (
1) derived from at least one aromatic diisocyanate, either unsubstituted or containing up to one methyl substituent on each aromatic ring, and (2) having at least 2 carbodiimide units per polycarbodiimide molecule. Therefore, the resulting molding resin composition has substantially improved impact strength.

However, none of the patents or applications that purport to stabilize or otherwise improve polyesters by reacting polyesters with carbodiimides disclose non-dripping reinforced flame retardant compositions.

It is therefore a general object of the present invention to avoid or substantially reduce the above-mentioned problems of the prior art.

A further object of the present invention is to provide a process for the preparation of reinforced flame-retardant copolyester compositions which are particularly free of dripping properties. Another object of the present invention is to provide a process for making flame retardant reinforced copolyester compositions suitable for forming three-dimensional articles with improved flame retardancy.

A further object of the present invention is to provide reinforced flame retardant copolyester compositions prepared by these methods.

Yet another object of the present invention is to provide a reinforced flame retardant copolyester composition which is free of asbestos and does not drip when exposed to flame.

Another object of the present invention is to provide an improved self-extinguishing copolyester molding resin composition capable of forming three-dimensional articles that pass the UL-flammability test.

Other advantages of the invention will become apparent from the description of preferred embodiments of the invention.

One feature of the present invention is a method for producing a reinforced flame-retardant copolyester molding resin composition that is non-dripping.

This method comprises at least one A-strengthening agent, at least one BVb-containing compound, and at least one alkane diol having 2 to 6 Cla carbon atoms.
Species, b Terephthalic acid, isoterephthalic acid, or dialkyl esters thereof in which the alkyl group has 1 to 7 carbon atoms, and formula C (wherein the aromatic nucleus of P, p'' isopropylidene diphenol is It is substituted with 1 to 4 halogen atoms, R represents a divalent hydrocarbon group having 2 to 6 carbon atoms, and m and n are integers of 1 to 10.

) is a copolyester consisting of a halogenated derivative of bishydroxyethyl ether of P,p''-isopropylidene diphenol, which is a halogenated derivative of bishydroxyethyl ether of P,p''-isopropylidene diphenol. a copolyester comprising from about 8 to about 4 percent by weight of the copolyester composition, and
T2a derived from at least one aromatic diisocyanate, either unsubstituted or with up to one methyl substituent on each aromatic ring, and b a carbodiimide having at least 3 carbodiimide units per polycarbodiimide molecule; At least one molten reaction product is intimately mixed to form a flame retardant, non-dripping reinforced copolyester molding resin composition.

Another feature of the invention is the reinforced flame retardant polyester molding resin composition made by this method.

The gist of the invention is that flame-retardant molding resin compositions comprising a reinforcing agent, a group Vb metal-containing compound, and a halogenated copolyester can be obtained by reacting the halogenated copolyester with one of a limited number of polycarbodiimides. The present invention consists in the discovery that a halogenated copolyester molding resin composition modified with a reinforced polycarbodiimide does not drip when exposed to flame, even though it does not contain asbestos.

As indicated above, the process of the present invention consists of reacting a molten copolyester with a polycarbodiimide and intimately mixing it with a toughening agent and a Group Vb metal-containing compound.

The reinforcing agent used in the present invention provides strength to the molded article.

Reinforcing agents that can be used include glass fibers (cut or continuous), graphite fibers, acicular calcium metasilicate, and the like.
Fibers suitable for the method of the invention are preferably non-combustible alone. Glass fibers are particularly suitable. Particularly good glass reinforcing fibers are those commercially available as E-glass (lime-aluminoporosilicate glass) and S-glass (magnesium aluminosilicate glass).
It is available as a continuous fiber with a circular cross section and a diameter of approximately 10 microns. Mixtures of reinforcing agents can also be used.

The group Vb metal-containing compounds used in the present invention include phosphorus, arsenic,
There are compounds of antimony or bismuth.

Preferred Group Vb metal-containing compounds are Group Vb metal-containing oxide compounds. Antimony oxide is a particularly suitable Group Vb metal-containing compound. Mixtures of two or more Group Vb metal-containing compounds can also be used.

The third important component used in the present invention is P with copolyester.
, p″-isopropylidene diphenol.

In this formula, x is the reaction product of 7 bromine and/or chlorine atoms and at least one carbodiimide. The copolyester itself comprises (a) at least one alkanediol having 2 to 6 carbon atoms, (b) terephthalic acid, isoterephthalic acid or a dialkyl ester thereof, and (c) P. It is a reaction product of the halogenated derivative of hydroxyethyl ether of p''-isopropylidene diphenol. The alkanediols useful in the preparation of the copolyesters may have from 2 to 6 carbon atoms. Ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 2,3-butanediol, 1,5 -pentanediol, 1,6-heptanediol, etc. Alkanediols having 3 or 4 carbon atoms are suitable.The acid used in the copolyester formation can be terephthalic acid, isothyrephthalic acid or their dialkyl esters. The alkyl group of the dialkyl ester has 1 to 7 carbon atoms and includes methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, etc. Dimethyl ester of terephthalic acid is preferable.Alkanediols and terephthalic acid, isoterephthalic acid Acids or their esters have the formula:
P,p''-isopropylidene diphenol having the following properties is reacted with a halogen derivative of bishydroxyethyl ether.

The aromatic nucleus of P, p''-isopropylidene diphenol can be substituted with 1 to 4 halogen atoms such as bromine and/or chlorine. Bromine substitution is preferred and tetrabrominated derivatives are particularly suitable. 0R is a carbon atom 2 to 6, preferably 2
It is a divalent hydrocarbon group with .

m and n are integers from 1 to 10, preferably 3 or less. Preferred halogenated conductors of bishydroxyethyl ether of P,p''-isopropylidene diphenol are of the formula: Particularly preferred halogenated derivatives of hydroxyethyl ether are 2,2-bis[3,5
-dibromo4-(2-hydroxyethoxy)phenyl]propane.

The halogenated derivative of the bishydroxyethyl ether of P,p'-isopropylidene diphenol generally comprises from about 8 to about 4 weight percent of the copolyester composition, preferably from about 10 to about 3 weight percent. Importantly, however, for the copolyester composition to have flame retardant properties, the amount of halogen in the copolyester should be from about 4 to about 1 weight percent. If chlorine is used instead of bromine, the amount of halogen must be increased somewhat. Halogenated derivatives and copolyesters of bishydroxyethyl ether of P,p''-isopropylidene diphenol useful in the present invention include, for example, U.S. Pat.
It can be produced by the method described in No. 617.

The polycarbodiimides which can be reacted with the above-mentioned copolyesters in the method of the invention are selected from a particularly limited group of types.

Not all polycarbodiimides improve the non-drop properties of reinforced polyesters when reacted with copolyesters. Conversely, (a) any aromatic diisocyroisomer which is unsubstituted or has up to one methyl substituent on each aromatic ring; derived from at least one species of anate and (
b) It has been discovered that only polycarbodiimides having at least 3 carbodiimide units per polycarbodiimide molecule give this desired result. More heavily substituted aromatic diisocyanes. These result in polycarbodiimides that do not have sufficient reactivity to react with polyalkylene terephthalate at the desired rate.

If polycarbodiimides having fewer than three carbodiimide units per polycarbodiimide molecule are brought into contact with copolyesters, the copolyester will sag upon exposure to flame. It is necessary that the polycarbodiimide be miscible with the copolyester in the melt.

Polycarbodiimides useful in the present invention generally have about 450
from about 10,00 to typically from about 800 to about 8,000
, preferably having a number average molecular weight of about 1,000 to about 6,500. Carbodiimides with molecular weights greater than about 10,000 cannot be used in this invention because they will not dissolve in the copolyester melt. Examples of polycarbodiimides useful in the present invention include poly(4,4''-diphenylmethanecarbodiimide), poly(3,3-dimethyl-4,4'-
Biphenylmethanecarbodiimide (to), poly(toluylenecarbodiimide-containing poly(p-phenylenecarbodiimide)), poly(m-phenylenecarbodiimide-containing poly(3)
, 3'-dimethyl-4,4''-diphenylmethanecarbodiimide and mixtures thereof.

Preferred polycarbodiimides include poly(toluylenecarbodiimide), poly(4,4''-diphenylmethanecarbodiimide) and mixtures thereof. Polycarbodiimides can be prepared in a manner well known to those skilled in the art, e.g. The aromatic diisocyanate compounds described above can be produced by heating in the presence or absence of a solvent.

Carbodiimide is produced by the generation of carbon dioxide gas. The polycarbodiimides useful in the present invention can be produced without the use of catalysts, but without catalysts the polycarbodiimides can be produced at high temperatures (approximately 30
(principal)) is required.

For certain polycarbodiimides, the use of such high temperatures produces large amounts of by-products and colorants. Therefore, polycarbodiimides are commonly used in U.S. Pat.
No. 2,663,737 and No. 3,755,24
Dirt and Monegre's J. Org. Chem. ,27,
3851 (1962), by heating isocyanates in the presence of a catalyst such as the phosphorus-containing catalysts described in 3851 (1962). Campbel et al., J. Amer. Chem. SOc. 84s
3673 (1962) are suitable catalysts. A particularly preferred catalyst is 1-ethyl-3-methyl-3-phosphorin-1 monoxide. Since isocyanates tend to react rapidly with water at high temperatures, the polycarbodiimide forming reaction is preferably conducted under an argon or other dry inert gas atmosphere to minimize the amount of water that comes into contact with the reactants.

Aromatic diisocyanates that can be used to produce the desired polycarbodiimide include, for example, toluylene diisocyanate,
4,4″-diphenylmethane diisocyanate, 3,3
"-dimethyl-4,4"-biphenylene diisocyanate, p-phenylene diisocyanate, m-phenylene diisocyanate, 3,3-dimethyl-4,4"-diphenylmethane diisocyanate, and mixtures thereof. Preferred aromatic diisocyanates are toluylene diisocyanate. isocyanate, 4,4''-diphenylmethane diisocyanate, and mixtures thereof. Aromatic diisocyanates are best used in essentially pure form, but may contain small amounts (i.e., less than about 2% by weight) of other compounds such as urea, amines, and trace amounts of water and/or acids. good.゜“What is toluylene diisocyanade? 2,4-
It is meant to include toluylene diisocyanate, 2,6-toluylene diisocyanate or any combination of these isomers. A mixture of 2,4- and 2,6 monoisomers is usually prepared by mixing 8 parts of 2,4-toluylene diisocyanate with 2,6 parts of 2,4-toluylene diisocyanate.
- Contains either 2 parts by weight of toluylene diisocyanate or 65 parts by weight of 2,4-toluylene diisocyanate and 35 parts by weight of 2,6-toluylene diisocyanate.

Aromatic monoisocyanates, in conjunction with aromatic diisocyanates, can also be used to prepare the polycarbodiimides used in the process of the invention.

The monoisocyanates help adjust the molecular weight and viscosity of the resulting polycarbodiimides. The amount of aromatic monoisocyanate used will depend on the particular diisocyanate used, but will generally be about 1.5 to about 5% monoisocyanate, usually about 2% by weight, based on the total weight of the isocyanate compound.
from about 4% by weight, preferably from about 2.5 to about 40% by weight
and a corresponding diisocyanate of from about 50 to about 9
8.5% by weight, usually about 55% to about 97.5% by weight, preferably about 60% to about 97.5% by weight. Aromatic monoisocyanates that can be used in this way include, for example, p-chlorophenyl isocyanate, m-chlorophenylisocyanate, phenyl isocyanate, p-methoxyphenyl isocyanate, m-methoxyphenyl isocyanate, p-tolyl isocyanate, -tolyl isocyanate, o-tolyl isocyanate, p-nitrophenyl isocyanate, m-nitrophenyl isocyanate, 2,6-diethylphenyl isocyanate and mixtures thereof.

Phenyl isocyanate, p-chlorophenylisocyanate, m-chlorophenylisocyanate and mixtures thereof are preferred monoisocyanates for use in the present invention. Polymerizable carbodiimides cannot be produced by heating monoisocyanates alone, so monoisocyanates alone cannot be used to produce polycarbodiimides.

Small amounts of certain high molecular weight phenoxy resins can also be used as heat aging agents in this invention.

The phenoxy resin used here is U.S. Patent No. 3,35
It is a high molecular weight thermoplastic resin produced from 2,2-bis(4-hydroxyphenyl)-propane and epichlorohydrin by the method described in No. 6,646. This resin has a repeating structure: from about 15,000 to about 75,000
It is characterized by having an average molecular weight of 0.00.

The terminal structure is completed with a hydrogen atom or a suitable terminal cap group. Other additives, both polymeric and non-polymerizable, such as lubricants, dyes, antioxidants and inorganic fillers can also be used as long as they do not interfere with the reaction of the polycarbodiimide and copolyester.

Generally, such additives may be included in amounts up to about 3% by weight of the total composition. reinforcing agent, group Vb metal-containing compound,
The relative amounts of copolyester and polycarbodiimide can vary over a wide range, but generally the reinforcing agent will generally be from about 15 to about 60% by weight, typically from about 20 to about 5% by weight, based on the total weight of the molding resin composition. , preferably from about 25 to about 45% by weight; Group Vb metal-containing compounds generally from about 0.7 to about 1%, typically from about 2 to about 7%, preferably from about 3 to about 6%; Polyester - generally about 30 to about 8 weight percent, typically about 4575 to about 75 weight percent, preferably about 50 to about 7 weight percent; and polycarbodiimide generally about 0.25 to about 5 weight percent. , typically about 0.35
from about 4% by weight, preferably from about 0.45 to about 3% by weight
can be used.

If the reinforcing agent is 60% or more, processing becomes difficult, but if it is 15% or less, the deflection coefficient becomes small and the heat deflection temperature becomes low.

If the amount of the group Vb metal-containing compound is 10% or more, the physical properties and appearance of the product will deteriorate, but if the amount of the compound is 0.7% or less, the product will be easily combustible.

When polycarbodiimide is used in an amount of 5% or more, the melt strength of the composition increases, making processing difficult.

If the amount of polycarbodiimide is less than about 0.25%, the composition will drip during a combustion test. The weight ratio of available halogen in the copolyester to available Group Ib metal in the Group Vb metal-containing compound is generally from about 0.3 to about 4, typically about 0. ω to about 3, preferably from about 0.46 to about 2.

The amount of phenoxy resin that is mixed is generally about 0.1 to about 1% by weight, typically about 0.1% to about 1% by weight, based on the total molding resin composition.
375 to about 8% by weight, preferably about 0.5 to about 3% by weight. The toughening agent, Group Vb metal-containing compound, copolyester, and polycarbodiimide may be mixed in any convenient manner so long as the polycarbodiimide is contacted with the molten copolyester for a sufficient period of time to effect the chemical reaction.

Ingredients can be dry mixed or melted! Mixing may also be done in an extruder, heated roller or other type of mixer. If necessary, the copolyester (or together with the reactants used to form the copolyester) and the polycarbodiimide, as long as the reinforcing agent and the Group Vb metal-containing compound do not affect the chemical reaction between the copolyester and the polycarbodiimide. It may be mixed inside. Various methods of mixing the toughening agent, Group Vb metal-containing compound, copolyester, and carbodiimide are then described. Copolyester, polycarbodiimide, Vb
Physical mixing of the group metal-containing compound and the reinforcing agent is described by Werler-Pfceidere.
r) Can be made directly in a melt screw extruder such as a ZSK twin screw extruder. However, this method is undesirable since the initially solid copolyester tends to cause the reinforcing agent (eg, glass fiber) to fracture. A good way to mix the copolyester, polycarbodiimide, group Vb metal-containing compound, and reinforcing agent is to add the copolyester through the hopper of an extruder and add the polycarbodiimide, Vb
The group metal-containing compound and the reinforcing agent are added to the extruder from below (for example, at the exhaust port or other side feed port of the extruder). The advantage of this method is that the copolyester melts by the time it reaches the extruder where the polycarbodiimide, Group Vb metal-containing compound, and reinforcement are added (e.g., at the exhaust port), minimizing wastage of the reinforcement. The purpose is to limit the Another method of mixing the toughening agent, copolyester, polycarbodiimide, and group Vb metal-containing compound is to first react the copolyester and polycarbodiimide in a blastograph, and then modifying the toughening agent and the group Vb metal-containing compound with the polycarbodiimide. This is a method of adding it to the copolyester.

However, the reaction of the copolyester with the polycarbodiimide increases the melt viscosity of the copolyester, and this increase is likely to result in wastage of the reinforcing agent if it is added later. The thermoplastic phenoxy resin is prepared in a reinforced copolyester molding resin composition by (1) mixing the phenoxy resin with the reinforcing agent prior to intimate mixing with the Group B metal-containing compound, the copolyester, and the polycarbodiimide; or (2) it can be added by intimately mixing the phenoxy resin with the reinforcing agent, the V-group metal-containing compound, the copolyester, and the polycarbodiimide at the same time. Other mixing methods can also be used. What is important is that a chemical reaction actually occurs between the copolyester and the polycarbodiimide.

Apparently, the polycarbodiimide combines with the various chains of the copolyester molecule to produce a high molecular weight, highly viscous polycarbodiimide modified copolyester. The increased viscosity of this high molecular weight copolyester tends to prevent dripping during combustion. The process of the present invention can be carried out at a temperature such that the copolyester remains molten for a sufficient period of time to allow reaction between the copolyester and the polycarbodiimide to occur.

The reaction temperature must be high enough so that the copolyester is in a molten state, but not so high that the copolyester or polycarbodiimide decomposes. At atmospheric pressure, this reaction generally occurs at about 220 to about 300°C, typically about 2
25 to about 275°C, preferably about 230 to 260°C
It can be carried out at a temperature of The pressure can be varied widely,
Low pressure, atmospheric pressure and high pressure can be used, with substantially atmospheric pressure being suitable.

The molten copolyester and polycarbodiimide must be in contact for a sufficient time for chemical reaction to occur.

The progress of the reaction is determined by the carboxylic acid end groups (CE) of the copolyester.
G) can be monitored by observing the decrease over time. Of course, reaction time is a function of temperature and reaction times sufficient to obtain the desired product in the process of the present invention generally range from about 1 to about 7 minutes, typically from about 1.25 to about 6.8 minutes, preferably about 1
．． 5 to about 6. (melt screw extruder).
Since mixing does not occur as much in a blastograph as it does in a melt screw extruder, reaction times in a blastograph are typically somewhat longer. The method of the invention can of course be carried out batchwise, continuously or semi-continuously.

The invention is further illustrated in the following examples.

All parts and percentages in the examples and specification are by weight unless otherwise indicated. Example 1 This example uses glass, Sb2OJl asbestos, phenoxy PKHH resin, 1,4-butanediol, dimethyl terephthalate, and 2,2-bis[3,5-dibromo-4-(2-hydroxy-ethoxy)phenyl]propane. 1 illustrates the preparation and product physical properties of various combinations of copolyester and poly(4,4-diphenylmethanecarbodiimide).

Test 1 consisted of (a) 1,4-butanediol, dimethyl terephthalate and 2,2-bis[3,5-dibromo4
-(2-hydroxyethoxy)phenyl]propane copolyester, (b) glass fiber, (c) Sb2
Figure 2 illustrates the properties associated with a composition consisting of O3 and (d) poly(4,4''-diphenylmethanecarbodiimide).

Test 2 illustrates the properties of the composition using twice the amount of polycarbodiimide in the Test 1 composition. Test 3 illustrates the properties of a composition using twice the amount of polycarbodiimide in addition to 1% by weight of Phaeoxy PKHH resin in the composition of Test 2. Test 4 was conducted for comparative purposes.

This illustrates the properties of the composition using Union Carbide's Callidria asbestos fibers (resin grade 144) in place of polycarbodiimide in the Test 3 composition. The glass reinforcement in each case is Owens Corning 41931162 cut stretched glass.

In each case, all composition components were added through the hopper of a 28 wft Werner Pleiderer twin-screw melt extruder with the following screw configuration: The tension and thrust bars were molded in a 2-112 oz. Stubbe screw syringe under the molding conditions listed in Table 1.

The molding composition was heated in the injection chamber of the molding machine.

The material was then injected in the form of a hot fluid into a relatively cold closed mold by either a high-pressure plunger or a reciprocating screw, and upon cooling for a while the molded article solidified to the extent that it could be removed from the mold without deformation. The superiority of the resulting glass fiber reinforced molded resin can be confirmed by the standard UL-94 flammability test described above. For example, a 4 x 112 x 1116 inch bar can be formed by injection molding. Attach the forming rod vertically to the clamp and place a cotton pad 12 inches below the bottom end of the rod. After applying the 314 inch blue flame of a natural gas Bunsen burner to the lower end of the rod, the burner was removed and the time taken for the flame to disappear was measured. Immediately apply the flame again for m seconds, remove it, and measure the time it takes for the flame to disappear again. For this rod to pass this test, (a) it must not burn for more than w seconds at any time after being exposed to the flame; (b) Total burning time 5 for one set of 5 rods.
Must not exceed @. and (c) do not drip the melt and ignite the cotton bud underneath. In the specification of the present invention, a given molded product is considered to be "non-drip" if no combustion droplets are formed when the flame is removed according to the above test.

In the specification of the present invention, a given molded product is considered to be "self-extinguishing" if it does not burn 108 or more after removing the flame according to the above test.The properties of the glass reinforced copolyester composition are shown in Table 2. They are shown together.

The results shown in Table 2 are approximately 0.0% based on the total weight of the composition.
The addition of 5% to about 2% by weight of poly(4,4''-diphenylmethane-carbodiimide) has been shown to produce a non-dripping, enhanced Moto-1 fire extinguishing composition without the addition of asbestos.

The molding compositions of the present invention can be readily molded into three-dimensional articles with sufficient mechanical properties using conventional molding techniques normally used for polypropylene terephthalate and polybutylene terephthalate. Either compression or injection molding methods can be used. The molding method used is preferred because it does not substantially fracture any reinforcing agent. The compositions of the present invention are particularly suitable for applications where a high degree of flame retardancy is required when formed into three-dimensional articles. For example, the compositions of the present invention are particularly suited for applications such as high temperature electrical appliances, diesel cartridge caps, terminal blocks, and various automotive hood components. The three-dimensional molded product formed from this composition is placed in a high-temperature environment, e.g.
Can be used at temperatures between 0 and 200°C. EXAMPLE 1 This example illustrates the preparation of polycarbodiimide used in the preparation of the glass-reinforced polycarbodiimide-modified copolyester composition of the present invention.

The special polycarbodiimides used are reaction products of aromatic diisocyanates and aromatic monoisocyanates.
A 500 mt resin reaction flask is equipped with a gas charging tube, a magnetic stirrer, and a condenser (Graham spiral loop), and at the top, the gas charging tube is connected to a bubbler that detects gas evolution. To this flask was added 105 fI of toluylene diisocyanate. 62.1y of p-chlorophenylisocyanate and 3f of bis(β-chloroethyl)vinylphosphite were added. This screw (
β-Chloroethyl) vinyl phosphate, commercially available from Stoffer Chemical Company under the trade name FurOlBisBeta, was used as a catalyst in this reaction. Argon was carefully passed over the reactant surfaces.

The flask containing the reactants was placed in an oil bath at about 190 C (internal reaction temperature is about 17075 to 18 CfC). The reaction was carried out while slowly passing argon. Within a few minutes of being placed in the oil bath, the limewater solution became cloudy and carbon dioxide bubbles were observed. The reaction continued for approximately 4 hours until a foam formed in the flask. Further heating was continued until the flask was mostly filled with foam. During this time, argon was passed rapidly over the surface. Heating was then stopped and the flask was cooled in an argon atmosphere. The reaction vessel containing the product was weighed and a weight loss of approximately 20% was observed. The foam was quite brittle and broke easily. The remaining dark red material could also be crushed or softened with acetone and removed. The product is converted into isocyanate (
4.4 μ) and a small peak for carbodiimide (4
．． It showed a large peak for 7μ) and a substantial peak probably for polymerized carbodiimide (6.0μ). The carbodiimide and polymerized carbodiimide mixture comprised about 90-95% of the product. The product was further purified by vacuum heating in a 205° C. oil bath for 21 h.

Weight loss varied by approximately 15% of the removed material. The final product was found to be 1R and free of isocyanate. It was also found that virtually all of the catalyst was removed by purification since the phosphorus concentration was less than 0.1%. This polycarbodiimide product was mixed with the copolyester, glass fiber, and Sb, O3 used in Test 1 (Example 1) in the same manner as in Test 1 of Example 1, and similar results were obtained.

COMPARATIVE EXAMPLE This comparative example describes an improved glass-reinforced copolyester composition containing (a) monocarbodiimide and (b)
Figure 2 illustrates the effect with highly substituted polycarbodiimides.

In this comparative test, the amounts, reaction conditions, equipment, and molding conditions were the same as in the test of Example 1, but instead of poly(4,4-diphenylmethanecarbodiimide), (a) p-chlorophenylcarbodiimide (monocarbodiimide) and (b ) poly(2,6-diisopropyl-1,3-phenylenecarbodiimide) (a highly substituted polycarbodiimide) was used.

In both cases there was virtually no improvement in the dripping properties of the glass-filled copolyester compositions compared to glass-filled copolyester compositions that did not contain polycarbodiimide.

The principles, preferred embodiments, and methods of operation of the invention are as described in the foregoing specification.

Claims (1)

[Scope of Claims] 1 A at least one reinforcing agent, B at least one group Vb metal-containing compound, and C 1
a At least one alkanediol having 2 to 6 carbon atoms, b terephthalic acid, isophthalic acid, or a dialkyl ester thereof whose alkyl group has 1 to 7 carbon atoms, and c Formula ▲ Numerical formula, chemical formula, table, etc. p, p'-isopropylidene diphenol (denoted by ▼)
In the formula, the aromatic nucleus of p,p'-isopropylidene diphenol is substituted with 1 to 4 halogen atoms, R represents a divalent hydrocarbon group having 2 to 6 carbon atoms, and m
and n are integers from 1 to 10. 8 to 4 of the copolyester composition, wherein the halogenated derivative of bishydroxyethyl ether of p,p'-isopropylidene diphenol is
0% by weight of a copolyester and 2 a derived from at least one aromatic diisocyanate, either unsubstituted or with up to one methyl substituent on each aromatic ring, and b for each polycarbodiimide molecule. 1. A flame-retardant reinforced copolyester molding resin composition with non-dripping properties, characterized in that it comprises an intimate admixture of at least one reaction product of a polycarbodiimide having at least 3 carbodiimide units. 2. The flame-retardant reinforced copolyester molding resin composition according to claim 1, which contains 15 to 60% by weight of reinforcing agent, based on the total weight of the reinforced copolyester molding resin composition. 3. The flame retardant reinforced copolyester molding resin composition according to claim 2, wherein the reinforcing agent is glass fiber. 4. The flame retardant reinforced copolyester molding resin composition according to claim 2, wherein the reinforcing agent is acicular calcium metasilicate. 5 The copolyester is (a) 1,4-butanediol,
Claim 3 consisting of (b) dimethyl terephthalate and (c) 2,2-bis[3,5-dibromo-4-(2-hydroxyethoxy)phenyl]propane.
The flame-retardant reinforced copolyester molding resin composition described in 1. 6 Polycarbodiimide is poly(toluylenecarbodiimide), poly(4,4'-diphenylmethanecarbodiimide), poly(3,3'-dimethyl-4,4'-biphenylmethanecarbodiimide), poly(p-phenylenecarbodiimide), poly (m-phenylenecarbodiimide), poly(3,3'-dimethyl-4,4'-diphenylmethanecarbodiimide), and mixtures thereof. Reinforced copolyester molding resin composition. 7. The flame retardant reinforced copolyester composition contains, based on its total weight, 15 to 60% by weight of reinforcing agent, 0.7 to 10% by weight of a Group Vb metal-containing compound, 30 to 80% by weight of copolyester, and 0.7 to 10% by weight of a group Vb metal-containing compound. A flame retardant reinforced copolyester molding resin composition according to claim 6, comprising 25 to 5% by weight of polycarbodiimide. 8 (a) (1) at least one alkanediol having 3 or 4 carbon atoms; (2) terephthalic acid, isophthalic acid or a dialkyl ester thereof, the alkyl group of which has 1 to 7 carbon atoms; and (3) ) Formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, X represents a bromine and/or chlorine atom.) p. A copolyester comprising a halogenated derivative of bishydroxyethyl ether of p'-isopropylidene-diphenol, the copolyester comprising p. A halogenated derivative of bishydroxyethyl ether of p'-isopropylidene diphenol was added to the copolyester composition.
10 to 75% by weight of copolyester containing 30 to 30% by weight
and (b) a reaction product of 0.35 to 4% by weight of a polycarbodiimide selected from the group consisting of poly(toluylenecarbodiimide), poly(4,4'-diphenylmethanecarbodiimide), and mixtures thereof;
20-50% by weight of seed strengthener and at least one V
A flame-retardant reinforced copolyester molding resin composition according to claim 1, which comprises intimately admixing 2 to 7% by weight of a Group B metal-containing compound. 9 The reinforcing agent is glass fiber, the Vb group metal-containing compound is Sb_2O_3, and the copolyester is (a)1,
4-butanediol, (b) dimethyl terephthalate,
and (c) 2,2-bis[3,5-dibromo-4-(
It is a reaction product of 2-hydroxyethoxy)phenyl]propane and polycarbodiimide is poly(4.4'
-diphenylmethanecarbodiimide), the flame retardant reinforced copolyester molding resin composition according to claim 8.