JP2002526585A - Halogen free flame retardant thermoplastic polymer composition - Google Patents

Abstract

  (57) [Summary] Halogen-free flame retarded polymer compositions comprise an ABS resin as the sole resin and P, P with two or less total hydrocarbyl substituents of 8 or less as the only phosphorus-containing flame retardant. Made using '-dihydrocarbylpentaerythrityl diphosphonate, or at least one thermoplastic polymer, and at least one of the above P, P'-dihydrocarbylpentaerythrityl diphosphonates and at least one It is made from a combination with at least one arylbis (dihydrocarbylphosphate) and / or at least one arylbis (dihydrocarbylphosphate). An effective flame retardant (UL-94 V-0) can be obtained without substantially impairing the physical properties required for the substrate polymer.

Description

DETAILED DESCRIPTION OF THE INVENTION

BACKGROUND OF THE INVENTION Hitherto, certain pentaerythrityl diphosphonates have been proposed for use in the preparation of certain polymer compositions. That is, US Pat. No. 3,141,032
It has been proposed to use as a flame retardant for polyolefins and cellulose acetate and C _{1 to 18} dialkyl pentaerythrityl phosphonate in No.. German Offenlegungsschrift 26 30 693 proposes the use of such a large group of diphosphonates as flame retardants for polyesters.

However, despite these earlier proposals, various pentaerythrityl diphosphonates have since been found to be ineffective as flame retardants in various polymeric materials. US Pat. No. 4,154,721 discloses di-C _1-8 alkyl or di-C ₆
No. _-20 arylpentaerythrityl diphosphonate is described as "independently effective in imparting recognizable flame retardant properties to a polymer composition ...".
According to this patent, the use of a halogenated organic compound containing at least about 30% halogen in combination with pentaerythrityl diphosphonate imparts suitable flame retardant properties to the polymeric substrate. The patent states that pentaerythrityl diphosphonate behaves as a synergist and has no effect on its own, but significantly enhances the flame retardant properties of the halogenated organic compounds used together. .

In US Pat. No. 4,162,278, di-C _8-18 alkylpentaerythrityl diphosphonate “has no effect of delaying the combustion of polyphenylene ether resin”; Dimethylpentaerythrityl diphosphonate, diphenylpentaerythrityl diphosphonate and dibenzylpentaerythrityl diphosphonate when used individually at a concentration of 8% by weight in high impact polystyrene modified with It was shown that seven different pentaerythrityl diphosphonates, including, failed the flammability test. This patent discloses that disubstituted pentaerythrityl diphosphonate is a blend of polyphenylene ether resin and rubber modified high impact polystyrene, where the two substituents are methyl, phenyl, benzyl or mono-, di- or trimethyl. It is reported that the effect of delaying combustion is as long as it is a benzyl group.

[0004] In US Pat. No. 4,174,343, "diphosphonates are non-dropping (nondrip) compounds which have a self-extinguishing property by themselves in polyolefins.
ping) are not useful in making polyolefin compositions. " In fact, in Examples 6 to 18 of the patent, dimethylpentaerythrityl diphosphonate, diphenylpentaerythrityl diphosphonate and dibenzylpentaerythrityl diphosphonate each contained 30% by weight alone in polypropylene. When used at a% concentration, it has been shown to have failed the UL94 vertical flame retardancy test. The patent uses a combination of pentaerythrityl diphosphonate (where each substituent on the phosphorus atom is a methyl, phenyl, benzyl or cyano group) and ammonium polyphosphate to obtain adequate flame retardancy in polypropylene are doing.

[0005] US Pat. No. 4,178,281 states that 4% dimethylpentaerythrityl diphosphonate in polycarbonate gave a V-0 rating in the UL-94 test. . However, in a 50-50 blend of polycarbonate and ABS, 10% of dimethylpentaerythrityl diphosphonate is UL-9.
Does not meet the requirements of flame retardancy in 4 tests. Dimethyl pentaerythrityl diphosphonate and diphenyl pentaerythrityl diphosphonate were tested in the UL-94 test at a concentration of 20% in a 50-50 blend of polycarbonate and ABS in the UL-94 test.
A rating of −0 and V-2 was obtained. However, in order to obtain the flame retardancy of a blend of polycarbonate and ABS, the patent states that "but most often these phosphonates are used in combination with a halogenated organic compound having a halogen content of at least about 30%. It is desirable ". In the discussion of the nature of the components used, it was stated that "up to 30% if the use of halogenated organic compounds is indicated, as in the case of a blend of polycarbonate and ABS.
Can be used. However, in order to obtain satisfactory flame retardant properties in general in combination with the phosphates and phosphates, the halogenated organic compounds must
It is not necessary to use more than 0%. It is described.

US Pat. No. 4,257,931 discloses the following. "Diphosphonates by themselves have not found utility in delaying the burning of poly (1,4-butylene terephthalate) and producing non-dripping compositions with self-extinguishing properties." To impart effective flame retardancy to poly (1,4-butylene terephthalate), melamine pyrophosphate and substituents have cyano, methyl, phenyl, benzyl or 1-4 methyl groups on the ring A combination with a disubstituted pentaerythrityl diphosphonate that is benzyl is used.

[0007] Due to environmental concerns regarding halogen-containing additives often used in polymeric materials, great efforts have been made in the search for halogen-free additives with effective flame retardancy. Similar considerations are made for antimony-containing additive components in polymer materials.

[0008] A point that must be considered separately from the problem of the effect on flammability is that it is necessary to obtain effective flame retardancy without significantly degrading the heat distortion temperature characteristics for a polymer based on ABS. That is. Because of the inherent plasticity of these polymers, many known phosphorus-based flame retardants lower the heat distortion temperature of ABS as evidenced by the lower VICAT temperature. Therefore, there is a need for an effective method for imparting flame retardancy to ABS polymers without significantly lowering the heat distortion temperature.

BRIEF SUMMARY OF THE INVENTION According to one aspect of the present invention, ABS resins are extremely effective without substantially lowering the heat distortion temperature of the polymer as reflected in the VICAT temperature. It has been found that excellent flame retardancy can be obtained. These advantageous results are achieved without the use of organic halogen-containing or other phosphorus-containing flame-retardant additives or synergistic agents such as ammonium polyphosphate or melamine pyrophosphate. This is made possible by using substituted pentaerythrityl diphosphonates. Thus, this aspect of the invention addresses the strong need or need in the art for flame retardancy without the use of organic halogen-containing materials, while at the same time providing a single phosphorus-containing material to achieve superior flame retardant properties. A composition is provided that can use only additives.
Indeed, this aspect of the invention can provide a very economical ABS resin composition that does not require any environmental considerations with respect to halogen-containing additives or antimony-containing components often used in polymeric materials. . Also, this aspect of the invention can provide a flame retardant ABS composition that does not substantially impair the physical properties required for end use.

Thus, according to this aspect of the invention, in one embodiment, the total number of carbon atoms in the two hydrocarbyl substituents is (a) an ABS resin, and (b) a flame-retarding amount. A halogen-free polymer composition comprising a blend made from at least one P, P'-dihydrocarbylpentaerythrityl diphosphonate of 8 or less, wherein (c) the ABS resin Is the only polymer component of the composition, and (d) one or more P, P′-dihydrocarbylpentaerythrityl diphosphonate is the only phosphorus-containing flame retardant component of the composition; (E
2.) The composition is provided without a phosphorus-containing or antimony-containing flame retardant synergist.

The second aspect of the present invention particularly relates to the use of one or more of the above P, P′-dihydrocarbylpentaerythrityl diphosphonates together with certain diphosphates or diphosphinates. In this way, excellent flame retardancy can be obtained,
It is based on the finding that an excellent balance is obtained between a high thermal deformation temperature, as reflected in the ICAT temperature, and a high impact strength, as reflected in the value of the Izod impact strength. In fact, the use of the appropriate amount and the appropriate relative proportions of diphosphate or diphosphinate together with P, P'-dihydrocarbylpentaerythrityl diphosphonate sacrifices the composition's fire resistance. The overall physical properties of the resulting flame-retardant polymer composition can be improved without aging.

Further, the advantageous results of the second aspect of the present invention can be obtained in various thermoplastic polymers by using a combination of these phosphorus-containing additives without the use of halogen-containing additive components. it can. That is, this aspect of the invention meets at least the need in the art for flame retardants, at least in the absence of organic halogen-containing materials, and in some cases the need, without sacrificing physical properties. Provided is a composition capable of achieving excellent flame retardancy. Indeed, this aspect of the invention can provide a very economical thermoplastic composition that does not require any environmental considerations regarding halogen-containing additives or antimony-containing components often used in polymeric materials. . Also, this aspect of the invention can provide a flame retardant thermoplastic composition that does not substantially impair the physical properties required for end use.

Thus, according to this aspect of the invention, in one embodiment, (a) at least one P having at least 8 carbon atoms in the two hydrocarbyl substituents is 8 or less.
, P'-dihydrocarbylpentaerythrityl diphosphonate, and (b
) At least one aryl bis (dihydrocarbyl phosphate) and / or
Or made from at least one arylbis (dihydrocarbyl phosphinate), wherein the weight ratio of (a) :( b) is 1: 1 to 20: 1, preferably 4;
A halogen-free flame retardant additive composition in the range of 6: 1 is provided. Preferably, this additive composition also does not contain antimony.

In another embodiment of this aspect of the invention, there is provided (i) at least one thermoplastic polymer and (ii) a flame retardant conferring amount of (ii) two hydrocarbyl substituents. At least one P, P'-dihydrocarbylpentaerythrityl diphosphonate having a total carbon number of 8 or less; and (b) at least one aryl bis (dihydrocarbyl phosphate) and / or at least one
(A) prepared from a species of aryl bis (dihydrocarbyl phosphinate)
Halogen-free flame-retardant polymer comprising a blend made from a combination having a weight ratio of: :( b) in the range of 1: 1 to 20: 1, preferably 4; A composition is provided. Preferably, the polymer composition also does not contain antimony.

The present specification and claims relate to the polymer formulations of the above embodiments of the present invention that can be molded or extruded (ie, through a mold) without further dilution with the substrate polymer. The term "amount that imparts flame retardancy" used in the range of (1) refers to (1) P, P when used as the only phosphorus-containing flame retardant component in relation to the first embodiment.
The amount of '-dihydrocarbylpentaerythrityl diphosphonate, and (2
2.) The combined total amount of aryl bis (dihydrocarbyl phosphate) and / or aryl bis (dihydrocarbyl phosphinate) used as phosphorus-containing flame retardant component combined in connection with the second aspect is in each case The phosphorus-containing flame retardant blended with such a phosphorus-containing flame retardant for a particular polymer and the test sample made from these blends is required to have a V-0 rating in the UL-94 test method. Means at least the minimum amount of That is, in these situations, an amount greater than such a minimum amount relative to the amount of polymer can be used, and this amount can be considered as an amount that provides flame retardancy. The amount of flame retardant contained should not be so great that a molded sample of substantially uniform composition with acceptable properties from each of the samples obtained from the resulting mixture can be made.
On the other hand, with respect to masterbatch or powder formulations to make finished articles, extruded or foamed articles, or products (articles) further diluted with other polymer stocks, the lowest " It is possible to use a phosphorus-containing flame retardant in an amount larger than the "amount giving flame retardancy".

[0016] Other embodiments of the invention will be apparent from the following description of the invention, and from the claims.

DETAILED DESCRIPTION OF THE INVENTION First Embodiment of the Invention As described above, in this embodiment of the invention, (a) ABS resin, and (b)
A) a flame retardant amount of at least one P, P'-dihydrocarbylpentaerythrityl diphosphonate having at least 8 total carbon atoms in the two hydrocarbyl substituents; A halogen-free polymer composition comprising: (c) the ABS resin is the only polymer component of the composition;
(D) one or more P, P'-dihydrocarbylpentaerythrityl diphosphonates is the only phosphorus-containing flame retardant component of the composition; and (e) the composition comprises a phosphorus-containing flame retardant synergist. Compositions are provided that do not include an agent or an antimony-containing flame retardant synergist.

The phosphonate used to implement this aspect of the invention can be named in various ways. For example, P, P'-dihydrocarbylpentaerythrityl diphosphonate, dihydrocarbylpentaerythritol diphosphonate, dihydrocarbylpentaerythrityl diphosphonate, and the like. The hydrocarbyl substituent on the phosphorus atom can be the same or different and can be a saturated or unsaturated aliphatic hydrocarbyl group, a saturated or unsaturated cycloaliphatic hydrocarbyl group, or an aromatic hydrocarbyl group, The requirement that the total carbon number of the two substituents be 8 or less must be fulfilled. Accordingly, such hydrocarbyl groups can be alkyl, alkenyl, cycloalkyl, cycloalkenyl, cycloalkylalkyl, aryl, alkaryl, or aralkyl groups having up to 7 carbon atoms. A single aryl, alkaryl, or aralkyl group that can be present is a phenyl, tolyl, or benzyl group; in the case of phenyl, other hydrocarbyl groups can have one or two carbon atoms However, if one group is tolyl or benzyl, the other group is methyl. Examples of symmetric dihydrocarbyl pentaerythrityl diphosphonates that can be used in practicing the present invention include dimethyl pentaerythrityl diphosphonate, diethyl pentaerythrityl diphosphonate, dipropyl pentaerythrityl diphosphonate. Phosphonate, diisopropylpentaerythrityl diphosphonate, dibutyl pentaerythrityl diphosphonate, diisobutyl pentaerythrityl diphosphonate, di-sec-butyl pentaerythrityl diphosphonate, di-t-butyl pentane Erythrityl diphosphonate, divinyl pentaerythrityl diphosphonate, diallyl pentaerythrityl diphosphonate, dipropenyl pentaerythrityl diphosphonate, di (2-butenyl) pentaeryth Pentaerythrityl di phosphonate, di (2-propynyl) pentaerythrityl phosphonate include dicyclopropyl carbinyl pentaerythrityl phosphonate, and similar compounds. Examples of asymmetric dihydrocarbylpentaerythrityl diphosphonates that can be used to practice the present invention include P-ethyl-P'-methylpentaerythrityl diphosphonate, P-ethyl-P'-butyl Pentaerythrityl diphosphonate, P-isobutyl-P'-methylpentaerythrityl diphosphonate, P
-Methyl-P'-vinylpentaerythrityl diphosphonate, P-allyl-
P'-pentylpentaerythrityl diphosphonate, P-methyl-P'-phenylpentaerythrityl diphosphonate, P-ethyl-P'-phenylpentaerythrityl diphosphonate, P-phenyl-P ' -Vinylpentaerythrityl diphosphonate, P-ethynyl-P'-phenylpentaerythrityl diphosphonate, P-methyl-P'-o-tolylpentaerythrityl diphosphonate, P-methyl-P ' -M-tolylpentaerythrityl diphosphonate, P-methyl-P'-p-tolylpentaerythrityl diphosphonate, P-benzyl-P'-methylpentaerythrityl diphosphonate, P-
Cyclohexyl-P'-methylpentaerythrityl diphosphonate, P-4
-Methylcyclohexyl-P'-methylpentaerythrityl diphosphonate, P-cyclohex-3-enyl-P'-methylpentaerythrityl diphosphonate, P-2-methylcyclopent-3-enyl-P '-Methylpentaerythrityl diphosphonate, and similar compounds, and mixtures of these two or more compounds are included. A preferred compound from the viewpoint of cost effectiveness is dimethylpentaerythrityl diphosphonate. Methods that can be used or applied for the production of such compounds are known and are described, for example, in US Pat.
Nos. 1,022 and 4,154,721.

In accordance with this aspect of the invention, component (b) is added to component (a) in an amount that provides flame retardancy.
(Or an ABS resin without a flame retardant), the resulting ABS composition gives a molded test sample that shows a V-0 rating when subjected to the known standard UL-94 test method. .

The ABS resin, the method for producing it, the method for molding, extruding and foaming it, and the molded articles and moldings (manufactured articles) that can be produced therefrom are known in the art and have been reported in the literature. Those who are interested in the above techniques for ABS are, for example, John Wiley and Sons, Inc. Published in 1963, Ki
rk Othmer, Encyclopedia of Chemical
Technology, Second Edition, Volume 1, pp. 338-351; John Wil.
eye and Sons, Inc. Published by Kirk Othmer in 1978, Encyclopedia of Chemical Technology
John Wiley and Son, 3rd Edition, Volume 1, pages 442-446;
s, Inc. Published in 1964, Encyclopedia of Polymer
r Science and Technology, Volume 1, 374-444
And other relevant references mentioned in the above cited pages of Encyclopedia. These documents are attached for reference. ABS resins suitable for practicing the present invention are available from a number of commercial products.

The following examples are for illustrative purposes and do not limit the invention. In these examples, all percentages are by weight unless otherwise specified.

Examples 1 and 2 and Controls CE-3 to CE-5 In a Brabender mixer at a temperature of 175.degree.
By mixing at 75 rpm for 5 minutes, ABS (Dow Chemica) was added.
l Co. Magnum PG) was blended with the additives at the ratio (pph) shown in Table 1. The blended resin is then compression molded, cut and 12.7 x 1.27 x about 0.
Bar-shaped test specimens measuring 159 cm (5 x 0.5 x 0.0625 inches) were made. Next, this test sample was subjected to a vertical combustion test according to the UL-94 method. Examples 1 and 2 are examples of the present invention, and Examples CE-3, CE-4 and CE-5 are shown for control purposes.

[0023]

[Table 1]

* Sample drip and burned cotton in one of 10 burns. ** Some samples burned for more than 30 seconds. No NR = UL rating. In a VICAT test (ASTM D 1525) performed on a sample having a thickness of about 0.318 cm (1/8 inch) under a load of 1 kg, Examples 1 and 2 were tested.
The ABS composition provided values of 107.5 ° C. and 105 ° C., whereas the untreated ABS had a value of 105.2 ° C. Therefore, the composition of the present invention did not show any deterioration in the heat deformation characteristics in these tests.

Second Aspect of the Invention This aspect of the invention is directed to a method of (a) wherein at least one P, P'-dihydrocarbyl penta, wherein the total number of carbon atoms in the two hydrocarbyl substituents is 8 or less. Erythrityl diphosphonate, and (b) at least one aryl bis (dihydrocarbyl phosphate) and / or at least one aryl bis (
Halogen-free flame-retardant additive made from dihydrocarbyl phosphinate) and having a weight ratio of (a) :( b) in the range of 1: 1 to 20: 1, preferably 4; Recall that it relates to an agent composition.

The phosphonate used in this aspect of the invention is any one of the phosphonates described above in relation to the first aspect of the invention, or any combination of two or more thereof. be able to.

At least one aryl bis (dihydrocarbyl phosphate) and / or
Alternatively, at least one arylbis (dihydrocarbyl phosphinate) constitutes another phosphorus-containing additive used to practice this aspect of the invention.
These compounds can be represented by the following general formula.

[0028]

Embedded image

Wherein each Z is a hydrocarbyl group which can be the same or different, or
Is a hydrocarbyloxy group which can be the same or different and Ar is divalent
Is an aromatic moiety. When the Z group is hydrocarbyl, the compound is an aryl
A bis (dihydrocarbyl phosphinate) wherein the Z group is a hydrocarbyl oxo
If the compound is an arylbis (dihydrocarbyl phosphate)
It is. Typically, the hydrocarbyl and hydrocarbyloxy groups are each
It contains 1 to 20, preferably 1 to 10, carbon atoms. Such hydro
Carbyl groups are alkyl, alkenyl, cycloalkyl, cycloalkenyl,
Aralkyl, cycloalkylalkyl, cycloalkylaryl, or
Similar hydrocarbyl groups can be used. Most preferably a hydrocarbyl group
Is aryl having 6 to 10 carbon atoms, particularly phenyl. The divalent aromatic moiety Ar is
It typically contains from 6 to 20 carbon atoms and is a monocyclic aromatic moiety such as a phenylene group.
) Or a polycyclic aromatic moiety, such as a biphenylene group (eg, -C₆H_Four-C₆H_Four−
), Naphthylene group (for example, -C_TenH₆-), Oxybiphenylene group (for example, -C₆ H_Four-OC₆H_Four-), Alkylene biphenylene group (for example, -C₆H_Four-RC₆H _Four -Wherein R is an alkylene having 1 to 4 carbon chains in total and having 1 to 6 carbon atoms in total.
Group) or similar groups. The aromatic moiety may include one or more hydro-
A carbyl group, for example an alkyl group, can be substituted. Aryl bis (di
Examples of (hydrocarbyl phosphate) include the following compounds. Resorci
Nol bis (dimethyl phosphate), resorcinol bis (diethyl phosphate)
Fate), resorcinol bis (dipropyl phosphate), resorcinol
Rubis (dibutyl phosphate), resorcinol bis (dioctyl phosphate)
), Resorcinol bis (divinyl phosphate), resorcinol
(Diallyl phosphate), resorcinol bis (dicyclohexyl phosphate)
Fate), resorcinol bis (dimethylcyclohexyl phosphate),
Resorcinol bis (dicyclohexenyl phosphate), resorcinol bi
(Dimethylcyclohexenyl phosphate), resorcinol bis (ditri
Resorcinol bis (dixylyl phosphate), resorcinol
Lucinol bis (diethyl phenyl phosphate), resorcinol bis (di
-1-naphthyl phosphate), resorcinol bis (di-2-naphthyl phosphate)
Sulfate), resorcinol bis (dibenzyl phosphate), resorcinol
Bis (di-2-methylbenzyl phosphate), resorcinol bis (di
-3-methylbenzyl phosphate), resorcinol bis (di-4-methyl)
Benzyl phosphate), resorcinol bis (diphenethyl phosphate)
), Resorcinol bis (di-α-methylbenzyl phosphate), resorcinol
Nol bis (dicyclopropylcarbinyl phosphate), hydroquinone bis
(Dimethyl phosphate), hydroquinone bis (diethyl phosphate),
Hydroquinone bis (dipropyl phosphate), hydroquinone bis (dibutyl
Phosphate), hydroxyquinone bis (dioctyl phosphate), hydroxy
Non-bis (divinyl phosphate), hydroquinone bis (diallyl phosphate)
), Hydroquinone bis (dicyclohexyl phosphate), hydroquinone
Bis (dimethylcyclohexyl phosphate), hydroquinone bis (dicyclo
Hexenyl phosphate), hydroquinone bis (dimethylcyclohexenyl sulfate)
Phosphate), hydroquinone bis (ditolyl phosphate), hydroquinone
Bis (dixylyl phosphate), hydroquinone bis (diethylphenyl phosphate)
Sulfate), hydroquinone bis (di-1-naphthyl phosphate), hydroquinone
Quinone bis (di-2-naphthyl phosphate), hydroquinone bis (dibenzyl
Rufosphate), hydroquinone bis (di-2-methylbenzylphosphate)
G), hydroquinone bis (di-3-methylbenzyl phosphate), hydroxy
Non-bis (di-4-methylbenzyl phosphate), hydroquinone bis (diph
Enetyl phosphate), hydroquinone bis (di-α-methylbenzyl phosphate)
Fate), hydroquinone bis (dicyclopropylcarbinyl phosphate)
, Catechol bis (dimethyl phosphate), catechol bis (diethyl phosphate)
Sulfate), catechol bis (dipropyl phosphate), catechol bis
(Dibutyl phosphate), catechol bis (dioctyl phosphate),
Catechol bis (divinyl phosphate), catechol bis (diallyl phosphate)
Fate), catechol bis (dicyclohexyl phosphate), catechol
Bis (dimethylcyclohexyl phosphate), catechol bis (dicyclohexylphosphate)
Xenyl phosphate), catechol bis (dimethylcyclohexenyl phosphate)
Fate), catechol bis (ditolyl phosphate), catechol bis (di
Xylyl phosphate), catechol bis (diethyl phenyl phosphate)
), Catechol bis (di-1-naphthyl phosphate), catechol bis (di
-2-naphthyl phosphate), catechol bis (dibenzyl phosphate)
), Catechol bis (di-2-methylbenzyl phosphate), catechol bi
(Di-3-methylbenzyl phosphate), catechol bis (di-4-methyl
Rubenzyl phosphate), catechol bis (diphenethyl phosphate)
Catechol bis (di-α-methylbenzyl phosphate), catechol bis
(Dicyclopropylcarbinyl phosphate), 1,1'-oxydiphenol
-4,4'-bis (dimethyl phosphate), 1,1'-oxydiphenol
-4,4'-bis (diethyl phosphate), 1,1'-oxydiphenol
-4,4'-bis (dibutyl phosphate), 1,1'-oxydiphenol
-4,4'-bis (diphenyl phosphate), 1,1'-oxydipheno
-3,3'-bis (dimethyl phosphate), 1,1'-oxydipheno
-3,3'-bis (diphenyl phosphate), 1,1'-oxydife
Nol-3,3'-bis (diallyl phosphate), 1,1'-oxydife
Nor-3,3'-bis (dicyclohexyl phosphate), 1,1'-oxo
Sidiphenol-2,2'-bis (dimethylphosphate), 1,1'-oxo
Sidiphenol-2,2'-bis (dicyclohexenyl phosphate), 1,
1'-oxydiphenol-2,2'-bis (diphenyl phosphate),
Tylene bisphenol bis (dimethyl phosphate), methylene bisphenol
Rubis (diphenyl phosphate), methylene bisphenol bis (dibenzi
Rufosphate), 4,4'-methylenebis (m-cresol) bis (dife
Nylphosphate), 4,4'-methylenebis (o-cresol) bis (diff
Phenyl phosphate), 4,4'-methylenebis (m-cresol) bis (di
Methyl phosphate), 4,4'-methylenebis (o-cresol) bis (di
Methylphosphate), 4,4'-methylenebis (m-cresol) bis (di
Benzyl phosphate), 4,4'-methylenebis (o-cresol) bis (
Dibenzyl phosphate), 2,2'-propylidene bisphenol bis (di
Methyl phosphate) (also known as bisphenol-A-dimethyl phosphate)
), 2,2'-propylidenebisphenol bis (diphenyl phosphate)
(Also known as bisphenol-A-diphenyl phosphate), 2,2'-propyl
Redene bisphenol bis (dibenzyl phosphate) (also known as bisphenol
-A-dibenzyl phosphate), 2,2'-propylidenebis (m-cre
Sol) bis (diphenyl phosphate), 2,2'-propylidenebis (o
-Cresol) bis (diphenyl phosphate), 2,2'-propylidenebi
(M-cresol) bis (dimethyl phosphate), 2,2'-propylide
Bis (o-cresol) bis (dimethyl phosphate), 2,2'-propyl
Redidenbis (m-cresol) bis (dibenzylphosphate), 2,2'-
Propylidenebis (o-cresol) bis (dibenzylphosphate), 1,
1'-ethylidenebisphenol bis (diphenyl phosphate), 1,1 '
-Propylidene bisphenol bis (diphenyl phosphate), benzylide
Bis (diphenyl phosphate), and similar compounds.

Examples of arylbis (dihydrocarbyl phosphinates) used to practice this aspect of the invention include the following compounds: Resorcinol bis (dimethylphosphinate), resorcinol bis (diethylphosphinate), resorcinol bis (dipropylphosphinate), resorcinol bis (dibutylphosphinate), resorcinol bis (dioctylphosphinate), resorcinol bis (divinyl) Phosphinate), resorcinol bis (diallylphosphinate), resorcinol bis (dicyclohexylphosphinate), resorcinol bis (dimethylcyclohexylphosphinate), resorcinol bis (dicyclohexenylphosphinate), resorcinol bis (dimethylcyclohexenyl) Phosphinate), resorcinol bis (ditolyl phosphinate), resorcinol bis (dixylyl phosphate) Sulfonate), resorcinol bis (diethyl phenyl phosphinate),
Resorcinol bis (di-1-naphthyl phosphinate), resorcinol bis (di-2-naphthyl phosphinate), resorcinol bis (dibenzyl phosphinate), resorcinol bis (di-2-methylbenzyl phosphinate), Resorcinol bis (di-3-methylbenzyl phosphinate), resorcinol bis (di-4-methylbenzyl phosphinate), resorcinol bis (diphenethyl phosphinate), resorcinol bis (di-α-methylbenzyl phosphinate) ), Resorcinol bis (dicyclopropylcarbinyl phosphinate), hydroquinone bis (dimethyl phosphinate), hydroquinone bis (diethyl phosphinate), hydroquinone bis (dipropyl phosphinate) Hydroquinone bis (dibutyl phosphinate), hydroquinone bis (dioctyl phosphinate), hydroquinone bis (divinyl phosphinate), hydroquinone bis (diallyl phosphinate), hydroquinone bis (dicyclohexyl phosphinate), hydroquinone bis (dimethylcyclohexyl) Phosphinate), hydroquinone bis (dicyclohexenyl phosphinate), hydroquinone bis (dimethylcyclohexenyl phosphinate), hydroquinone bis (ditolyl phosphinate), hydroquinone bis (dixyl phosphinate), hydroquinone bis (diethyl) Phenylphosphinate), hydroquinone bis (di-1-naphthylphosphinate), hydroquinonebis (di-2-naphthylphosphine) ), Hydroquinone bis (dibenzylphosphinate), hydroquinone bis (di-2-methylbenzylphosphinate), hydroquinone bis (di-3-methylbenzylphosphinate), hydroquinone bis (di-4-methyl) Benzyl phosphinate), hydroquinone bis (diphenethyl phosphinate), hydroquinone bis (di-α-methylbenzyl phosphinate), hydroquinone bis (dicyclopropylcarbinyl phosphinate), catechol bis (dimethyl phosphinate) ), Catechol bis (diethyl phosphinate), catechol bis (dipropyl phosphinate), catechol bis (dibutyl phosphinate), catechol bis (dioctyl phosphinate), catechol bis (divinyl phosphinate) Catechol bis (diallylphosphinate), catecholbis (dicyclohexylphosphinate), catecholbis (dimethylcyclohexylphosphinate), catecholbis (dicyclohexenylphosphinate), catecholbis (dimethylcyclohexenylphosphinate) Catechol bis (ditolyl phosphinate), catechol bis (dixylyl phosphinate), catechol bis (diethyl phenyl phosphinate), catechol bis (di-1-naphthyl phosphinate), catechol bis (di- 2-naphthyl phosphinate), catechol bis (dibenzyl phosphinate), catechol bis (di-
2-methylbenzyl phosphinate), catechol bis (di-3-methyl benzyl phosphinate), catechol bis (di-4-methyl benzyl phosphinate), catechol bis (diphenethyl phosphinate), catechol bis ( Di-α-methylbenzyl phosphinate), catechol bis (dicyclopropylcarbinyl phosphinate), 1,1′-oxydiphenol-4,4 ′
-Bis (dimethylphosphinate), 1,1'-oxydiphenol-4,4
'-Bis (diethylphosphinate), 1,1'-oxydiphenol-4,
4'-bis (dibutylphosphinate), 1,1'-oxydiphenol-4
, 4'-bis (diphenylphosphinate), 1,1'-oxydiphenol-3,3'-bis (dimethylphosphinate), 1,1'-oxydiphenol-3,3'-bis ( Diphenylphosphinate), 1,1′-oxydiphenol-3,3′-bis (diallylphosphinate), 1,1′-oxydiphenol-3,3′-bis (dicyclohexylphosphinate), 1,1'-
Oxydiphenol-2,2'-bis (dimethylphosphinate), 1,1 '
-Oxydiphenol-2,2'-bis (dicyclohexenylphosphinate), 1,1'-oxydiphenol-2,2'-bis (diphenylphosphinate), methylenebisphenolbis (dimethylphosphinate) ), Methylenebisphenolbis (diphenylphosphinate), methylenebisphenolbis (dibedylphosphinate), 4,4′-methylenebis (m-cresol) bis (diphenylphosphinate), 4,4′-methylenebis (o) -Cresol) bis (diphenylphosphinate), 4,4'-methylenebis (m-cresol) bis (dimethylphosphinate), 4,4'-methylenebis (o-
Cresol) bis (dimethylphosphinate), 4,4'-methylenebis (m
-Cresol) bis (dibenzylphosphinate), 4,4′-methylenebis (o-cresol) bis (dibenzylphosphinate), 2,2′-propylidenebisphenolbis (dimethylphosphinate) (also known as , Bisphenol-A-dimethylphosphinate), 2,2'-propylidenebisphenolbis (diphenylphosphinate) (also known as bisphenol-A-diphenylphosphinate), 2,2'-propylidenebisphenolbis (diphenylphosphine) Benzyl phosphinate) (also known as bisphenol-A-dibenzyl phosphinate), 2,2′-propylidenebis (m-cresol) bis (diphenylphosphinate), 2,2′-propylidenebis (o-cresol) bis (Diphenylphosphinate), 2,2 ' Propylidenebis (m-cresol) bis (dimethylphosphinate), 2,2′-propylidenebis (o-cresol) bis (dimethylphosphinate), 2,2′-propylidenebis (m-cresol) bis (dibenzylphosphonate) Finate), 2,2'-propylidenebis (o-
Cresol) bis (dibenzylphosphinate), 1,1'-ethylidenebisphenolbis (diphenylphosphinate), 1,1'-propylidenebisphenolbis (diphenylphosphinate), benzylidenebis (diphenylphosphinate) And similar compounds.

For ease of reference, P, P′-dihydrocarbylpentaerythrityl diphosphonate will hereinafter often be referred to generally as “phosphonate”, and arylbis (dihydrocarbyl phosphate) will generally be referred to as “phosphate”. The aryl bis (dihydrocarbyl phosphinate) will be generally referred to as "phosphinate".

Phosphonate (a) vs. phosphate and / or phosphinate (
The relative proportions of b) are typically in the range of 1 to 20 parts by weight of phosphate per part by weight of phosphate and / or phosphinate (b). Preferably, the weight ratio of (a) :( b) is such that (a) is 1 to 10 parts by weight per 1 part by weight of (b). More preferably, the weight ratio of (a) :( b) is such that (a) is 4 to 6 parts by weight per 1 part by weight of (b). Most preferably, the weight ratio of (a) :( b) is (
b) 5 parts by weight per part by weight of (a). When (b) is a combination of a phosphate and a phosphinate, the relative proportion between the phosphate and the phosphinate is between the case where one is a trace and the other is a trace. Is an arbitrary ratio. In other words, the phosphate and the phosphinate can be used in any and all proportions to one another.

[0033] The thermoplastic polymers to which the additive of the present invention can be added include the following polymers. Polystyrene; two or more styrene monomers, for example, copolymers of styrene, vinyl toluene, ethyl styrene, t-butyl styrene, α-methyl styrene, vinyl naphthalene, etc .; Homopolymers or copolymers (eg high impact polystyrene); ABS, thermoplastic polyesters such as polyethylene terephthalate, polybutylene terephthalate,
Thermoplastic polyamides such as polytrimethylene terephthalate and polycyclohexylene terephthalate, such as nylon 6, nylon 66 and nylon 6,12; polycarbonates, polyphenylene oxides such as poly (2,6-dimethylphenylene oxide); polysulfones; For example, polyethylene, polypropylene, poly (1-butene), ethylene and one or more higher vinyl olefins such as propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene Polymers; blends or composites of different polymers, such as blends of poly (2,6-dimethylphenylene oxide) and polystyrene, and similar materials. Numerous thermoplastic polymers without additives suitable for use in practicing this aspect of the invention can be obtained from commercial sources. Suitable thermoplastic polymers for use in practicing the present invention are ABS and styrene polymers, especially high impact polystyrene.

The ABS polymer composition of this aspect of the invention can be in the form of a pre-blend (eg, a powder blend) of components (a) and (b), which can be prepared at a suitable temperature and pressure. Molding or extrusion can be performed under the conditions to form a molded article or molded product under either expanded (expanded) or non-expanded (non-expanded) conditions. Similarly, the composition can be a molded or extruded product or the molded article itself. Further, the ABS polymer composition of this aspect of the present invention comprises the component (b)
Can be in the form of a masterbatch or a concentrated pre-formulation whose concentration is higher than the intended concentration in the final finished molding or molded product to be produced. Such a masterbatch and concentrated pre-blend may be mixed or blended with another ABS material as a dry material or a melt blend, which may then be molded or extruded into a finished molded article or molded product. it can.

The polymer composition of this aspect of the invention may comprise (A) at least one phosphate, and (B) at least one phosphate or (C) at least one phosphinate, or (D) In the form of a pre-formulation (e.g. a powder formulation) consisting of a combination of at least one phosphate and at least one phosphinate, which is formed or extruded under suitable temperature and pressure conditions. It can be formed into a molded article or molded product under any of the following conditions: expanded (expanded) or not expanded (not expanded). Similarly, the composition can be a molded or extruded product or the molded article itself. Also, the polymer composition of this aspect of the invention may be a masterbatch or concentrate in which the concentration of the flame retardant is higher than the intended concentration in the final finished molded article or molded article to be produced. It can be in the form of a pre-mix. Such a masterbatch and the concentrated pre-blend can be mixed or blended with another polymer as a dry material or a melt blend, which can then be molded or extruded into a finished molded body or molded product. it can.

In accordance with a second aspect of the present invention, the flame retardant is a thermoplastic polymer (ie, containing no halogen-containing flame retardant additive, preferably no antimony-containing additive component) in a flame-retardant amount. When incorporated into a (thermoplastic polymer), the resulting polymer composition provides a molded test sample that exhibits a V-0 rating when tested according to the known UL-94 test method. In making the formulation, the individual flame retardants can be separately compounded with the matrix polymer. However, (A) at least one phosphate, and (B) at least one phosphate or (C) at least one phosphinate, or (D) at least one phosphate and at least one phosphate. It is preferred to use a premix consisting of a combination of finates in the compounding operation. In this way, the tendency of malfunction during compounding is reduced, and compounding operations are generally easier.

The following examples relating to the second aspect of the present invention are intended to be illustrative and not limiting. In these examples, proportions are given in parts by weight per 100 parts by weight (pph).

Examples 3 to 5 and Controls CE-6 to CE-9 Rotating the rotor at a temperature of 175 ° C. in a Brabender mixer with a speed of 50 to 50 ° C.
By mixing at 75 rpm for 5 minutes, ABS (Dow Chemica) was added.
l Co. Magnum PG) was blended with the additives at the ratio (pph) shown in Table 2. The blended resin is then compression molded, cut and 12.7 x 1.27 x about 0.
Bar-shaped test specimens measuring 159 cm (5 x 0.5 x 0.0625 inches) were made. Next, this test sample was subjected to a vertical combustion test according to the UL-94 method. Examples 3-5 are examples of the present invention, and Examples CE-6-CE-9 are provided for control purposes.

[0039]

[Table 2]

A number of test samples were prepared from various formulations as in Examples 6 and 7, and Controls CE-9 through CE-12 Examples 1-3, and standard physical property determinations were made. . The materials tested and the test results are shown in Table 3. Examples 6 and 7 illustrate the invention. Examples CE-9-CE12 are shown for control purposes. The flame retardant used in Example CE-12 is a known flame retardant system containing a commercially available halogen and antimony.

[0041]

[Table 3]

Both Embodiments of the Invention The flame-retardant polymer composition of the individual embodiments of the present invention comprises the particular flame retardant of the particular embodiment in an amount that provides 3-50% by weight of the flame retardant. The finished polymer composition comprises, but in most cases, the upper limit for this amount is 40% by weight (therefore, the composition may be 3 to 4% by weight).
It is more desirable to have a flame retardant in the range of 40% by weight), and often the upper limit of this amount is 30% by weight (therefore the composition contains a flame retardant in the range of 3 to 30% by weight). More desirable. For certain embodiments, no matter what chemical form or composition such a flame retardant is present in the resin of a particular embodiment of the matrix, the finished composition preferably has a composition of 10%. -40% by weight, most preferably 20-3%
It contains usable phosphorus-containing flame retardants in the range of 0% by weight. These weight percentages are based on the sum of the usable resin used in making the compounded composition and the usable phosphorus-containing flame retardant, and are used to make up the finished polymer composition. Are the values excluding the amounts of the components. As mentioned above, one method of producing such a polymer composition is to use a higher available phosphorus-containing concentration than the concentration to be included in the available substrate resin and final finished product. This is a method using a masterbatch made from a flame retardant or a pre-mixed composition rich in additives. Such masterbatch or additive-rich pre-combined compositions typically comprise from 20 to 90 parts by weight of the usable phosphorus-containing flame retardant per 100 parts by weight of the base resin and the phosphorus-containing flame retardant used. A melt blended masterbatch or powder blend made from Such masterbatch and additive-rich pre-blend compositions form another embodiment of the present invention, in which a suitable amount of masterbatch or additive-rich pre-blend is prepared by adding the flame retardant component. Formulate with the appropriate amount of the same substrate, free of any, and form a formulation with the final use proportion of the phosphorus-containing flame retardant used in the substrate, no matter what form it is present after compounding together It can be used to make finished polymer compositions. It should be noted that in the first aspect of the invention, the ABS resin is the only polymer component of the composition and dihydrocarbylpentaerythrityl diphosphonate is the only phosphorus-containing component of the composition. is there. In the second aspect of the present invention, the flame retardant used is (1) at least one dihydrocarbylpentaerythrityl diphosphonate and (2) at least one arylbis (dihydrocarbyl phosphate) or At least one arylbis (dihydrocarbylphosphate), or at least one arylbis (dihydrocarbylphosphate) and at least one arylbis (
It should be noted that the substrate polymer or resin is the only thermoplastic polymer or combination of thermoplastic polymers.

No halogen-containing additives are intentionally added to the compositions of the present invention. Therefore, the composition of the present invention does not contain any halogens other than the materials (solvents, catalysts, etc.) used in the synthesis or production, the impurities generated from the process or the process equipment. Typically, the additive composition, e.g., a masterbatch or pre-blend, if any, of the flame retardant component that can be used to make the finished polymer of the present invention according to the present invention. Contains no more than about 1000 parts by weight (ppmw) of halogen impurities per million parts by weight. Thus, the term "halogen-free" in relation to such additive compositions contained is about 100, if any, present.
It means that only 0 ppmw or less of halogen is contained. The finished polymer composition of the present invention typically contains no more than about 100 parts by weight of halogen impurities per million parts by weight of the total polymer composition. Thus, the term "halogen free" as used herein in reference to the finished polymer composition means that it contains no more than about 100 ppmw, if any, of halogen. Generally, in preparing resins or foams made from the polymer compositions of the present invention, these compositions contain less than this amount of halogen unless a halogen-containing solvent or gas is used. .

Similarly, in a preferred embodiment, no additives including antimony are intentionally added to the compositions of the present invention. Such preferred compositions may contain traces of antimony, such as those found by chance, that may have been incorporated into the polymer formulation by fouling the compounding equipment with the antimony additive. It does not contain components containing antimony other than impurities such as antimony oxide previously used in such devices.

Yet another embodiment of the present invention is a method of imparting flame retardancy to a polymer of a usable substrate, the method comprising the steps of providing a flame retardant that can be used in the resulting polymer composition. Is a method of incorporating the flame retardant into the polymer such that the polymer composition, regardless of its chemical composition and form, contains an amount of the phosphorus-containing flame retardant that provides flame retardancy. . As noted above, such a polymer composition can provide a test sample that exhibits a V-0 rating in the UL-94 test method. The step of incorporating the usable flame retardant of the present invention into a usable substrate polymer can be performed before or during the production of the polymer. For example, such components can be added to the monomers or to the polymerization system used to make the polymer. Similarly, a flame retardant can be added to the polymerization mixture during the polymerization reaction itself. However, it is preferred to add the flame retardant of the present invention to a usable polymer after the polymer has been prepared. Further, the addition can be carried out stepwise before and during the polymerization, before and after the polymerization, during and after the polymerization, or before, during and after the polymerization.

Other ingredients, such as extrusion aids (eg, barium stearate or calcium stearate), impurity removers (eg, magnesium oxide or tetrasodium pyrophosphate), dyes, pigments, fillers, stabilizers, antioxidants, charging Inhibitors, reinforcing materials and the like can be included in the polymer composition of the present invention. When the polymer composition of the present invention is designed as an expanded or expanded polymer material, it may include a nucleating agent (eg, talc, calcium silicate, or indigo) to control pore size. Is desirable. The particular materials chosen in using the compositions of the present invention should not substantially adversely affect the properties of the finished polymer composition for the intended use.

Various known methods can be used for preparing the formulations or compositions that constitute this aspect of the invention. For example, the components to be incorporated in the finished formulation can be compounded in powder form and then extruded, compressed or molded by injection molding. Similarly, Banbury mixer, Brabender mixer, roll mill,
After mixing the components in a kneader, or other similar mixing device, it can be extruded, for example, into the desired shape or form, and then ground into granules or pellets, or using other methods. it can.

The compositions of the present invention can be used in the manufacture of useful products of the type normally produced by molding or extruding conventional flame retarded polymers. It is likewise possible to produce foamed or expanded moldings or articles from the compositions according to the invention. Molding and extrusion conditions such as temperature and pressure are usually within the recommended ranges. The conditions commonly used to produce foamed or expanded moldings or articles from flame retarded thermoplastic polymers may be used with little or no change in the compositions of the present invention. it can.

Each component or component referred to anywhere in the specification and claims may be admixed with, mixed with, one or more other components, whether or not it is singular or plural. Or it shall define the substance in the chemical form and composition that existed at least prior to compounding. It does not matter what chemical changes, rearrangements and / or reactions take place in the mixture itself. This is because such changes, rearrangements, and / or reactions are a natural consequence of placing certain components or components under the conditions described herein. Also, although the claims may state a substance in its present form (eg, "comprises" or "being"), a substance may be referred to initially as one or more other substances in accordance with the description herein. It should be understood that reference is made to the form as it existed immediately before contacting, blending or mixing. The fact that, according to the description herein, the substance may lose its original identity due to chemical reactions, complexation, solvation, ionization or other transformations during the course of the contacting, compounding or mixing operation. Also fall within the scope and limitations of the present invention.

[Procedural Amendment] Submission of translation of Article 34 Amendment of the Patent Cooperation Treaty

[Submission date] September 5, 2000 (2009.5)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Claims

[Correction method] Change

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[Claims]

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0038

[Correction method] Change

[Correction contents]

Examples 6 to 10 and Controls CE-11 to CE-12 Rotating the rotor at a temperature of 175 ° C. in a Brabender mixer with a speed of 50 to 50 ° C.
By mixing at 75 rpm for 5 minutes, ABS (Dow Chemica) was added.
l Co. Magnum PG) was blended with the additives at the ratio (pph) shown in Table 2. The blended resin is then compression molded, cut and 12.7 x 1.27 x about 0.
Bar-shaped test specimens measuring 159 cm (5 x 0.5 x 0.0625 inches) were made. Next, this test sample was subjected to a vertical combustion test according to the UL-94 method .

[Procedure amendment 3]

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[Correction target item name] 0039

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[0039]

[Table 2]

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[0040]Examples 13-16 and Controls CE-17 and CE-18 Example13-16Making a large number of test samples from various formulations as in
Standard physical property determinations were made. The materials tested and the test results are shown in Table 3. . Real Example CE-18The flame retardants used in the test were known commercial halogen and antimony.
It is a flame retardant system containing.

[Procedure amendment 5]

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[Table 3]

──────────────────────────────────────────────────続 き Continuation of front page (81) Designated country EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE ), CA, IL, JP PF terms (reference) 4F071 AA12X AA22 AA22X AA34X AA75 AA76 AC15 AE07 AF47 BB03 BC06 4J002 BB001 BB031 BB051 BB121 BB171 BC031 BC041 BC081 BC091 BN141 BN1103 CN1 CF011 001 EW137 FD136 FD137

Claims (50)

[Claims] 1. A halogen-free, flame-retardant polymer composition comprising: (I) an (A) ABS resin; and (b) a flame-retardant-deficient amount of two hydrocarbyl-substituted polymers. Comprising a formulation made from at least one P, P'-dihydrocarbylpentaerythrityl diphosphonate wherein the total number of carbon atoms in the group is less than or equal to 8; (D) the one or more P, P'-dihydrocarbylpentaerythrityl diphosphonates is the only phosphorus-containing flame retardant component in the composition; Or (ii) the composition does not comprise a phosphorus-containing flame retardant synergist and an antimony-containing flame retardant synergist; (II) the composition comprises (f) at least one thermoplastic polymer; And (g) the amount of (I) at least one P, P′-dihydrocarbylpentaerythrityl diphosphonate having a total number of carbon atoms of 8 or less in two hydrocarbyl substituents, and (ii) at least one aryl bis (di Hydrocarbyl phosphate) and / or at least one arylbis (dihydrocarbyl phosphinate), wherein the weight ratio of (i) :( ii) is in the range of 1: 1 to 20: 1. A halogen-free flame-retardant polymer composition, characterized in that it is a composition consisting of a blend according to claim 1. 2. The composition is subjected to the conditions (c), (d) and (e) (a)
2. The composition according to claim 1, wherein the composition is made from)) and (b). 3. The composition according to claim 1, wherein said formulation is made from (f) and (g). 4. The method according to claim 1, wherein said amount is not more than 30% by weight.
A composition as described. 5. The composition according to claim 1, wherein the composition is a melt-blended masterbatch or a powder pre-blend. 6. A molded, extruded, foamed or expanded molded article or product made from the composition according to claim 1. 7. The diphosphonate used to make the composition is dimethylpentaerythrityl diphosphonate, and the amount of diphosphonate used to make the composition is 30% by weight. % Or less. 8. The weight ratio of (a) :( b) on a weight basis is 70: 30-7.
3. The composition according to claim 1, wherein the composition is in the range of 5:25. 9. The composition according to claim 3, wherein (ii) is at least one aryl bis (dihydrocarbyl phosphate). 10. The composition according to claim 3, wherein (ii) is resorcinol bis (diphenyl phosphate). 11. (ii) is 2,2′-propylidenebisphenol bis (
4. The composition according to claim 3, wherein the composition is diphenyl phosphate). 12. The composition according to claim 3, wherein (ii) is at least one aryl bis (dihydrocarbyl phosphinate). 13. The composition according to claim 3, wherein (ii) is resorcinol bis (diphenylphosphinate). 14. The composition of claim 1, wherein the diphosphonate used to make the formulation is dimethylpentaerythrityl diphosphonate.
The composition according to any one of claims 4 to 8 or 13. 15. The composition according to claim 3, wherein (f) is a vinyl aromatic polymer. 16. The composition according to claim 3, wherein (f) is high impact polystyrene. 17. The composition according to claim 3, wherein (f) is ABS. 18. The composition according to claim 3, 9 to 13 or 15 to 17, wherein the composition does not contain antimony. 19. A molded, extruded, foamed or expanded molded article or product made from the composition according to claim 3, 9-13 or 15-17. 20. The composition according to claim 1, wherein the weight ratio of (i) :( ii) is in the range of 4: 1 to 6: 1. . 21. (f) is polystyrene, a copolymer of two or more styrene-based monomers, a rubber-modified vinyl aromatic homopolymer or copolymer, or A
The composition according to claim 3, 9 to 13, or 15 to 17, which is BS. 22. The composition according to claim 21, wherein the weight ratio of (i) :( ii) is in the range of 4: 1 to 6: 1. 23. A process for producing a halogen-free flame-retardant polymer composition, comprising: (I) (a) (1) a halogen-containing flame retardant, (2) a phosphorus-containing flame retardant, and (3)
A) not containing any of the flame retardant synergists containing phosphorus or antimony
BS, and (b) a flame-retardant amount of a P, P'dihydrocarbylpentaerythrityl diphosphonate having a total carbon number of two hydrocarbyl substituents of 8 or less, or such a diphospho And (c) the ABS resin is the only polymer component of the composition; and (d) one or more P, P'-dihydrocarbylpentanes. Erythrityl diphosphonate is the only phosphorus-containing flame retardant of the composition; (e) the composition is free of phosphorus-containing and antimony-containing flame retardant synergists Or (II) (f) a thermoplastic polymer, and (g) a flame-retardant-deficient amount of (i) at least one P which has no more than 8 carbon atoms in the two hydrocarbyl substituents. , P'-dihydroca Combination of a virupentaerythrityl diphosphonate with (ii) at least one arylbis (dihydrocarbylphosphate) and / or at least one arylbis (dihydrocarbylphosphinate), wherein (i) :( A process wherein a formulation is made from a combination wherein the weight ratio of ii) is in the range of 1: 1 to 20: 1, wherein the formulation is free of halogen-containing flame retardants. 24. The method of claim 23, wherein said composition is made by blending (a) and (b) together according to (c), (d) and (e). 25. The method of claim 23, wherein said composition is made by formulating (f) and (g) together. 26. The method according to claim 23, wherein the compounding is carried out while the polymer used is in the form of a molten polymer. 27. The polymer and phosphorus-containing flame retardant used are in the form of a powder or granules, and the polymer and phosphorus-containing flame retardant used are compounded while in the form of a powder or granules. The method according to claim 23, wherein the method is performed. 28. The method according to claim 25, wherein (ii) is resorcinol bis (diphenyl phosphate), resorcinol bis (diphenyl phosphate) or 2,2′-propylidene bisphenol bis (diphenyl phosphate). The described method. 29. The method according to claim 23, wherein the diphosphonate used is dimethylpentaerythrityl diphosphonate. 30. A process for the production of a flame-retardant shaped article or product, comprising: (I) (a) ABS, and (b) a flame-retardant amount of the total carbon number of the two hydrocarbyl substituents. Formulating together at least one P, P 'dihydrocarbylpentaerythrityl diphosphonate having a value of 8 or less, wherein (c) the ABS resin is the sole polymer component of the composition; C) one or more P, P'-dihydrocarbylpentaerythrityl diphosphonates is the only phosphorus-containing flame retardant of the composition; and (e) the composition is a phosphorus-containing flame retardant synergist. And forming a halogen-free compounded composition made without the antimony-containing flame retardant synergist, or (II) (f) a thermoplastic polymer, and (g) a flame retardant. (I) 2 pieces of given amount At least one P, P′-dihydrocarbylpentaerythrityl diphosphonate having a total number of carbon atoms of 8 or less in the hydrocarbyl substituent, and (ii) at least one arylbis (dihydrocarbyl phosphate) and / or Or containing a halogen, formed from a combination with at least one arylbis (dihydrocarbyl phosphinate) wherein the weight ratio of (i) :( ii) is in the range of 1: 1 to 20: 1. A method comprising molding a blended composition that does not include a flame retardant. 31. The method according to claim 30, wherein the shaped body or shaped article is made by shaping (a) and (b) according to (c), (d) and (e). . 32. The method according to claim 30, wherein said shaped body or shaped article is made by shaping (f) and (g). 33. The method according to claim 32, wherein (ii) is resorcinol bis (diphenyl phosphate), resorcinol bis (diphenyl phosphinate) or 2,2′-propylidene bisphenol bis (diphenyl phosphate). The described method. 34. The method according to claim 30, wherein the diphosphonate used is dimethylpentaerythrityl diphosphonate. 35. A method of extruding a halogen-free molten composition through a die to produce an extruded article or product having flame retardancy, comprising: (I) (a) ABS, and (b) A flame retardant-defining amount of a formulation comprising at least one P, P'dihydrocarbylpentaerythrityl diphosphonate having a total carbon number of two hydrocarbyl substituents of 8 or less, wherein (C) the ABS resin is the only polymer component of the composition; and (d) one or more P, P'-dihydrocarbylpentaerythrityl diphosphonates is the only phosphorus-containing component of the composition. (E) the composition is made from a formulation made without a phosphorus-containing flame retardant synergist and an antimony-containing flame retardant synergist; or (II) f) a thermoplastic polymer; and (g) at least one P, P'-dihydrocarbylpentane having a flame retardant amount, wherein (i) the total number of carbon atoms in the two hydrocarbyl substituents is 8 or less. A combination of erythrityl diphosphonate with (ii) at least one arylbis (dihydrocarbylphosphate) and / or at least one arylbis (dihydrocarbylphosphinate), wherein (i): (ii) Wherein the weight ratio is in the range of 1: 1 to 20: 1. 36. The molded article or product is produced using a blend of (a) and (b) made according to (c), (d) and (e). 35. The method of claim 35. 37. The method of claim 35, wherein said shaped body or product is made using a blend of (f) and (g). 38. The method according to claim 37, wherein (ii) is resorcinol bis (diphenyl phosphate), resorcinol bis (diphenyl phosphate) or 2,2′-propylidene bisphenol bis (diphenyl phosphate). The described method. 39. The method according to claim 37, wherein (f) is high impact polystyrene or ABS. 40. The process according to claim 35, wherein the diphosphonate used is dimethylpentaerythrityl diphosphonate. 41. The method according to claim 23,25,28,30,32,33,35, wherein the weight ratio of (i); (ii) is in the range of 4: 1 to 6: 1. 37. The method according to 37-39. 42. (f) is polystyrene, a copolymer of two or more styrene monomers, a rubber-modified vinyl aromatic homopolymer or copolymer, or A
42. The composition according to claim 41, which is BS. 43. (i) at least one P, P′-dihydrocarbylpentaerythrityl diphosphonate wherein the total number of carbon atoms of the two hydrocarbyl groups is 8 or less; and (ii) at least one arylbis (Dihydrocarbyl phosphate) and / or at least one arylbis (dihydrocarbyl phosphinate) in a weight ratio of (i) :( ii) of 1: 1 to 20:
A halogen-free flame-retardant additive composition, characterized in that it comprises a compound made from the combination according to claim 1. 44. The formulation comprises at least one P, P′-dihydrocarbylpentaerythrityl diphosphonate wherein the total carbon number of the two hydrocarbyl groups is 8 or less, and at least one aryl bis (diphenyl 44. The composition according to claim 43, which is made from hydrocarbyl phosphate). 45. The formulation comprises at least one P, P'-dihydrocarbylpentaerythrityl diphosphonate wherein the total carbon number of the two hydrocarbyl groups is 8 or less, and at least one arylbis (dihydrocarbyl) 44. The composition of claim 43, wherein the composition is made from a phosphinate. 46. The method according to claim 43, wherein (ii) is resorcinol bis (diphenyl phosphate), resorcinol bis (diphenyl phosphinate) or 2,2′-propylidene bisphenol bis (diphenyl phosphate). A composition as described. 47. The composition according to claim 43, wherein (i) is pentaerythrityldimethyl diphosphonate. 48. The composition according to claim 43, wherein said composition does not contain antimony. 49. The composition according to claim 48, wherein (i) is pentaerythrityldimethyl diphosphonate. 50. The composition according to claim 43, wherein the weight ratio of (i) :( ii) is in the range of 4: 1 to 6: 1.