CN102634170A - Low-gas-quantity halogen-free flame retardant thermoplastic polyester composition - Google Patents
Low-gas-quantity halogen-free flame retardant thermoplastic polyester composition Download PDFInfo
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Abstract
The invention discloses a low-gas-quantity halogen-free flame retardant thermoplastic polyester composition which is characterized by comprising the following components in parts by weight: 25-65 parts of at least one poly-terephthalic acid alkylene ester, 1-15 parts of at least one copolyester with a specific structure, 1-30 parts of at least one aromatic phosphate ester shown by a formula (I), and 1-30 parts of at least one selected from phosphinate with structure shown by a formula (II) and/or diphosphinate with the structure shown by a formula (III). The copolyester with the specific structure is added into the composition, so that the combination of high fire resistance, high mechanical performance and low gas quantity can be realized, and the quantity of sediment is reduced in the molding process, especially the injection molding process; therefore, the production stability and the production efficiency can be improved, and the low-gas-quantity halogen-free flame retardant thermoplastic polyester composition is widely applied to the electrical and electronic industry.
Description
Technical field
The invention belongs to polymeric material field, be specifically related to a kind of low gas vol halogen-free flame-retardant thermoplastic polyester compsn.
Background technology
Thermoplastic polyester; Like polybutylene terephthalate (PBT), PTT (PTT) and polyethylene terephthalate (PET) excellent mechanical property and electric property are arranged; Especially PBT has very excellent shaping processability, very is widely used in the fields such as electronic electric equipment, housed device, business automation equipment, automobile and mechanical means.
In order to prevent and reduce the generation of fire, these application often require polyester to have excellent flame-retardant performance.The most frequently used method of giving the macromolecular material flame retardant resistance is to introduce fire retardant, comprises halogenated flame retardant and halogen-free flame retardants.Wherein, the general flame retarding efficiency of halogenated flame retardant is higher, and addition is less relatively, and is less to the influence of the mechanical property of macromolecular material, but can produce a large amount of poison gas in the combustion processes, and has problem such as environmental pollution.International related tissue and part country have begun to limit the use of halogenated flame retardant; California, USA in 2008 with in August, 2004 European Union put into effect relevant rule, ban use of the halogenated flame retardant-pentabromodiphenyl oxide and the octabromodiphenyl ether that once were widely used.2009, the U.S. announced in next three years, progressively to eliminate decabromodiphenyl oxide, the non-halogen new trend that is just becoming the flame retarded polymeric material development once more.
Also there are some problems in bittern-free flame-proof material aspect development and application but at present.Such as comparing with halogenated flame retardant, the general flame retarding efficiency of halogen-free flame retardants is low, and addition is big, and big etc. to the macromolecular material performance impact.Therefore, for halogen-free, flame-retardant composition, desire under equal flame retardant rating, the prescription that development mechanics performance and halogen series flame retardant material compare favourably is difficult relatively.
The technician is generally through composite different fire retardant, and the optimization proportioning, and with the balance of acquisition flame retardant resistance and mechanical property, but mechanical property is generally not ideal enough.In the domestic patent, have, add second component resin in addition, improve the example of the resistance to impact shock of compsn as toughner through the one-tenth charcoal ability that adds the second resin Composition enhancing composition, the example that improves flame retardant resistance.Chinese patent CN1245443C (publication number) for example in flame retardant polyester composition, has added the aliphatic carboxylic acid of carbonatoms 10～40 and ester that fatty alcohol forms or acid amides as softening agent, improves the flowability of compsn.Do not add other resin Compositions but below all relate to or point out how to pass through, further improve the mechanical property of compsn.Especially, in U.S. Pat 20090088512A1, the method that adding polycarbonate (PC) can improve halogen-free flame-retarded polyester composition flame retardant resistance and mechanical property is disclosed.It is a flame-retardant system with organic secondary phosphine acid salt and Melamine Polyphosphate MPP, behind the PC of adding 5～10%, has not only strengthened the flame retardant resistance of compsn, has improved mechanical property simultaneously.
We further study and show, after PC added, the gas vol of compsn also significantly increased.As everyone knows, in the product injection molding process, high gas vol can make the mould joint face, and particularly accumulation more settling in venting port position stops up venting port, and it is difficult that injection moulding becomes.Particularly for thin wall parts, imposing a condition down, plastic melt is difficult to be full of die cavity again, or empyreumatic phenomenon takes place easily, and scrap rate can improve like this.In addition, high gas vol can cause extrude with injection moulding process in the effusion of a large amount of gases, contaminate environment.
Summary of the invention
The objective of the invention is to address the above problem, a kind of halogen-free, flame-retardant composition of giving thermoplastic polyester high flame retardant, strong mechanical performance and low gas vol is provided.The present invention has added the copolyesters with ad hoc structure in halogen-free flame-retarded polyester composition, reduced the gas vol of compsn, has realized the combination of high flame retardant, strong mechanical performance and low gas vol.
In order to solve the problem of mentioning in the background technology; We have carried out a large amount of research, and the result finds in halogen-free flame-retardant system, adds multipolymer or its mixture that main chain is made up of specific structure unit; When can and improve the compsn mechanical property in the enhancing composition flame retardant resistance; Reduce gas vol, alleviate environmental pollution, enhance productivity and job efficiency.
The object of the invention can reach through following measure:
A kind of low gas vol halogen-free flame-retardant thermoplastic polyester compsn is characterized in that:
(A) at least a polyalkylene terephthalates of 25-65 weight part,
(B) at least a copolyesters with ad hoc structure of 1-15 weight part,
(C) at least a aromatic phosphoric ester with structure shown in the formula (I) of 1-30 weight part,
(D) at least a diphosphinic acid salt that is selected from the phosphinates of the structure shown in (II) that has formula and/or has a structure shown in (III) of 1-30 weight part is formed;
The copolyesters with ad hoc structure described in above-mentioned (B) is to be selected from one or more diprotic acid and the product that (b) is selected from one or more divalent alcohol copolyreaction shown in formula (b1), formula (b2), formula (b3), formula (b4) and/or the formula (b5) in terephthalic acid or the m-phthalic acid by (a):
R in the formula
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8, R
9, R
10, R
11, R
12, R
13, R
14, R
15, R
16, R
17And R
18Be the alkyl of Wasserstoffatoms or C1-C5 independently respectively;
The structural formula of (I) is described in above-mentioned (C):
Ar1, Ar2, Ar3 and Ar4 be not respectively independently for replacing or substituted not halogen-containing aromatic base n in the formula
1Be the integer of 0-5, Y is the not halogen-containing arylidene shown in formula (c1), formula (c2) or the formula (c3):
R wherein
19, R
20, R
21, R
22, R
23, R
24, R
25And R
26Be the alkyl of Wasserstoffatoms or C1-C5 independently respectively, Z representes direct key, O, S, SO
2, CH
2Or C (CH
3)
2
(II) and structural formula (III) are respectively described in above-mentioned (D):
R in the formula
27, R
28, R
29And R
31For identical or different, and be alkyl and/or the aryl of hydrogen, straight chain or the C1-C6 that has side chain; R
30Be the alkylidene group of C1-C10 straight or branched, arylidene, alkyl arylene and/or the aryl alkylene of C6-C10; M, N are identical or different, and are earth alkali metal class, basic metal class, aluminium, zinc, titanium, zirconium, silicon, tin and/or a kind of protonated nitrogen base; M, m ' are identical or different, and are the integer of 1-4; n
2It is the integer of 1-4; X is the integer of 1-4.
Component of the present invention (A) polyalkylene terephthalates; Consider industrialization degree and share of market, preferably from (A-1) polybutylene terephthalate (PBT), (A-2) PTT (PTT) and/or (A-3) one or more in the polyethylene terephthalate (PET).
(A-1) polybutylene terephthalate (PBT) is with terephthalic acid and 1, and the 4-butyleneglycol is a main monomer, and the diacid or the glycol that add other are comonomer, and the multipolymer that polyreaction obtains also can mix 2 kinds or above different PBT use;
(A-2) PTT (PTT) is with terephthalic acid and 1, and ammediol is a main monomer, and the diacid or the glycol that add other are comonomer, and the multipolymer that polyreaction obtains also can mix 2 kinds or above different PTT use;
(A-3) polyethylene terephthalate (PET) is to be main monomer with terephthalic acid and terepthaloyl moietie, and the diacid or the glycol that add other are comonomer, and the multipolymer that polyreaction obtains also can mix 2 kinds or above different PET and use.
The total addition level of polyalkylene terephthalates (A) is the 25-65 weight part; Preferred 30-60 weight part, if the addition of polyalkylene terephthalates is lower than 25 weight parts, the mechanical property of compsn then; Comprise that tensile strength, flexural strength and shock strength are very low; Do not have actual application value, and if the addition of polyalkylene terephthalates is higher than 65 weight parts, then can not obtain high flame retardant resistance.
Preferably by (a) terephthalic acid and the product that (b) is selected from one or more divalent alcohol copolyreaction of structure shown in formula (b1), formula (b3) and/or the formula (b5), wherein (b1), (b3) and structure (b5) are respectively component (B):
R in the formula
1, R
2, R
5, R
6, R
7, R
8, R
15, R
16, R
17And R
18Be the alkyl of Wasserstoffatoms or C1-C5 independently respectively.
Component (B) also can be to be main monomer with (a) terephthalic acid with one or more divalent alcohol that (b) are selected from structure shown in formula (b1), formula (b3) and/or the formula (b5), and the diacid or the glycol that add other are comonomer, the multipolymer that polyreaction obtains.
In business-like product, component (B) can be selected: the U-polymer related prods of Japanese Unitika Corp (Unitika Ltd.), like P series, U is serial and AX series etc.; Specific examples such as U-100, P-1001, P-3001; P-5001, P-1001A, P-3001S; U8400, U8400S, AX-1500 or the like; The Copolyester of U.S. Eastman Chemical Company
series; Specific examples such as TX1000; TX1001, TX2000, TX2001; TX1500HF, TX1501HF or the like.Said product is merely indivedual instances, but component (B) is not limited to said product.
The introducing of component (B) has strengthened the flame retardant properties of compsn, has improved the mechanical property of compsn, has reduced gas vol simultaneously.Its total consumption is the 1-15 weight part, if consumption is lower than 1 weight part, the improvement of performance is not obvious; If consumption surpasses 15 weight parts, then flame retardant resistance can descend on the contrary.
Among the present invention, component (C) is preferably 0.1～15 with the ratio of the gross weight umber of component (D), further is preferably 0.2～12.Ratio is lower than 0.1, means that then the phosphinates addition is higher, possibly cause the compsn mechanical property bad, and cost is higher; Ratio is higher than 15, means that the SULPHOSUCCINIC ACID ESTER addition is higher, possibly cause the anti-exudative of compsn to descend.
Component of the present invention (C) is taken all factors into consideration from flame retardant properties, mechanical property and cost aspect; In two (diphenyl phosphoester) (hereinafter to be referred as the RDP) of preferred Resorcinol, two (diphenyl phosphoester) (hereinafter to be referred as the BDP) of dihydroxyphenyl propane, Resorcinol two [two (2, the 6-3,5-dimethylphenyl) SULPHOSUCCINIC ACID ESTER] and/or the Resorcinol two (diphenylphosphine acid phenenyl ester) one or more.Wherein, the structural formula that above-mentioned four kinds of aromatic phosphoric esters are corresponding is respectively like (c4), (c5), (c6) with (c7):
Resorcinol two (diphenyl phosphoester)
Dihydroxyphenyl propane two (diphenyl phosphoester)
Resorcinol two [two (2, the 6-3,5-dimethylphenyl) SULPHOSUCCINIC ACID ESTER]
Resorcinol two (diphenylphosphine acid phenenyl ester)
Component (C) also can be to satisfy structural formula (I) and have different n
1The mixture of the oligopolymer of value and/or the aromatic phosphoric ester of different structure.
The total addition level of aromatic phosphoric ester (C) is considered from flame retardant resistance and mechanical property aspect, selects the 1-30 weight part for use, preferred 3-28 weight part, more preferably 5-25 weight part.If total addition level is lower than 1 weight part, then need add more (D) component to reach higher flame retardant rating; And if total addition level is higher than 30 weight parts, then not only can reduces the anti-exudative of compsn, and can reduce the mechanical property of compsn dramatically.
Component of the present invention (D) is one or more in diethylammonium phospho acid calcium, diethylammonium phospho acid zinc and/or diethylammonium phospho acid aluminium preferably.
The total addition level of component (D) phosphinates and/or diphosphinic acid salt is considered from fire-retardant, mechanics and cost aspect, selects the 1-30 weight part for use, preferred 3-25 part.If total addition level is lower than 1 weight part, then the flame retardant resistance of compsn does not reach requirement; And if total addition level is higher than 30 weight parts, then cost can significantly increase, and the mechanical property of compsn also can reduce.
Can also contain component (E) 0-35 weight part melamine cyanurate in the compsn of the present invention.Selectable components of the present invention (E) melamine cyanurate is the affixture of the acid of cyanogen urea or isocyanuric acid and trimeric cyanamide, and CAS No. is 37640-57-6, and available general known method prepares, and can directly use also and can after surface treatment, re-use.
In this compsn, component (E) melamine cyanurate is auxiliary fire retardant.Can not add, but take all factors into consideration, preferably add, and preferably addition is the 1-35 weight part, more preferably the 3-30 weight part from flame retardant resistance, mechanical property and cost aspect.The adding of melamine cyanurate can further improve the flame retardant resistance of compsn, if but addition surpasses 35 weight parts, and the mechanical property of compsn can significantly reduce.
Can also contain component (F) 0-40 weight part fortifying fibre in the compsn of the present invention.Selectable components fortifying fibre of the present invention (F) is selected one or more in spun glass, thomel, basalt fibre and the aromatic polyamide fibre for use, both can use short fiber, also can use long fibre, preferred E alkali-free glass fiber.Component (F) can not added, but in order to improve the mechanical property of compsn, preferably interpolation and preferred addition are the 1-40 weight part, and more preferably the 5-35 weight part if be higher than 40 weight parts, then can influence the flame retardant resistance of compsn.
In the present invention, can further add an amount of mineral filler.Optional filler is one or more in mica, talcum powder, hydrotalcite, kaolin, polynite, silicon-dioxide, Calucium Silicate powder, calcium metasilicate, lime carbonate, magnesiumcarbonate, permanent white, titanium oxide, hollow glass bead, graphite, glass flake or the clay.These mineral fillers can two or morely be used simultaneously.Above-mentioned filler also can be handled with one or more surface treatment agent of coupling agent, organism and inorganics etc., preferably carries out surface treatment with coupling agent such as silane coupling agent, titanate coupling agent or aluminate coupling agent with known method.In addition, if select the filler that has nano-grade size or have sheet structure in the above-mentioned filler for use, can improve flame retardant resistance to a certain extent.The addition of filler can add according to the demand of cost or mechanical property, should not surpass 25 weight parts.If surpass 25 weight parts, the mechanical property of compsn can significantly reduce.
In addition; Can be as required; Exceed to add and use the known material that in thermoplastic resin, adds, for example anti-dripping agent, hydrolysis-resisting agent, inhibitor, the reagent of avoiding light or ultraviolet light degradation, lubricant, releasing agent, tinting material, nucleator and softening agent etc. usually not damage the present invention.
The anti-dripping agent of generally selecting for use is a tetrafluoroethylene, can add the 0.1-2 weight part, and its raising to flame retardant resistance is helpful; Hydrolytic resistance is poor because the ester bond of SULPHOSUCCINIC ACID ESTER easily hydrolysis takes place in addition, in compsn, can adopt the method for disclosed interpolation lime carbonate of patent CN100360595C and epoxy compounds to improve its hydrolytic resistance.It is functional that the use of these auxiliary agents can improve some of compsn, but what influence its basic flame retardant properties and mechanical property are not had basically, can select general these commercially available auxiliary agents for use, and they are not necessary for the present invention.The consumption of these auxiliary agents can add by conventional amount used according to the purpose of adding auxiliary agent.
In the present invention, also can further cooperate other to be prone to the flame retardant resistance that fire-retardant resin further improves said composition, these are prone to fire-retardant resin and comprise ppe and/or polyphenylene sulfide.
Halogen-free flame-retardant thermoplastic polyester compsn of the present invention adopts general known method to make.For example be selected from the phosphinates of the structure shown in (II) that has formula and/or have diphosphinic acid salt, (E) melamine cyanurate (selectable components), the mineral filler of structure shown in (III) or comprise that also other auxiliary agent joins the forcing machine from main hopper after the pre-mixing together at least a aromatic phosphoric ester, (D) with structure shown in the formula (I) of at least a copolyesters, (C) with ad hoc structure of (A) at least a polyalkylene terephthalates, (B) is at least a; Again (F) fortifying fibre (selectable components) is joined from the side feeding and melt extrude the forcing machine, be prepared into the halogen-free flame-retardant thermoplastic polyester compsn.
The halogen-free flame-retardant thermoplastic polyester compsn that obtains like this can adopt general method to carry out moulding, for example injection moulding, extrude, the method for mold pressing etc., wherein preferred injection moulding.
Halogen-free flame-retardant thermoplastic polyester compsn of the present invention; Can be widely used in the electronic enterprises; Such as the parts in electricinstallation, housed device, business automation equipment, automobile and the mechanical means, specifically can be used for housing, coil stand, coil housing and the coil support body of isolating switch, rly., junctor, X-former housing, lamp socket, plug, socket, derailing switch, charger, cooling air impeller, cooling air impeller.
The inventive method is simple to operate, the compsn environmental friendliness of preparation, and realized the combination of high flame retardant, strong mechanical performance and low gas vol.
Embodiment
The present invention will explain with reference to following embodiment and Comparative Examples in more detail, but these examples do not limit the scope of the invention.
Embodiment and Comparative Examples have been used following component.
(A) polyalkylene terephthalates
(A-1) polybutylene terephthalate PBT, 1100M, toray Co., Ltd.;
(A-2) PTT PTT, 503WS, U.S. Shell Co. Ltd;
(A-3) polyethylene terephtalate, SB50, Yizheng Chemical Fibre Co., Ltd..
(B) contrast is with resin and have the copolyesters of ad hoc structure
(B1) has the copolyesters of ad hoc structure
(B1-1) copolyesters: TX1000, U.S. Eastman Chemical Company;
(B1-2) polyarylester (PAR): U-100, Japanese You Niji can (Unitika) Co., Ltd.;
(B2) resin is used in contrast
(B2-1) polycarbonate (PC): IR2500, Japanese Idemitsu Petrochemical Co., Ltd..
(C) aromatic phosphoric ester
(C-1) PX200: two [two (2, the 6-3,5-dimethylphenyl) SULPHOSUCCINIC ACID ESTER] oligopolymers of Resorcinol,
Big eight KCCs of Japan;
(C-2) RDP: Resorcinol two (diphenyl phosphoester), Israel chemical industry group;
(C-3) BDP: dihydroxyphenyl propane two (diphenyl phosphoester), Israel chemical industry group;
(D) phosphinates and/or diphosphinic acid salt
(D-1) organic phospho acid zinc:
OP 950, German Clariant Co., Ltd;
(D-2) organic phospho acid aluminium:
OP 1240, German Clariant Co., Ltd;
(E) melamine cyanurate
(E-1) melamine cyanurate MCA:MC4000, Japanese Nissan KCC;
(F) fortifying fibre
(F-1) short glass fiber: 3J948, diameter 10 μ m, long 3mm, Co., Ltd. is spun in day east by Japan;
(G) mineral filler
(G-1) lime carbonate: spherical, 500 orders, Haicheng Jinghua Minerals Co., Ltd;
(G-2) mica: sheet, 500 orders, newly can be global mica material ltd;
(H) anti-dripping agent: tetrafluoroethylene
(H-1) PTFE:A3800, polytetrafluoroethylene powder, Mitsubishi Li Yang Co., Ltd.;
(I) oxidation inhibitor
(I-1) IR1010, Ciba (China) ltd.
Performance test methods:
Flame retardant resistance (vertical combustion method)
Standard batten with injection moulding is good is tested by standard UL94.Concrete is, Bunsen burner is placed the batten lower end of vertical placement, and igniting 10S removes burning things which may cause a fire disaster then, the record sample flaming combustion time; Certainly put out in the 30S after removing flame like sample; Then once more Bunsen burner is placed batten lower end igniting 10S; Whether the record burning things which may cause a fire disaster is removed back sample flaming combustion time and the flameless combustion time, observe simultaneously whether to produce molten drop and molten drop and ignite and be put in the absorbent cotton below the batten, and each sample is got 5 battens and is one group and tests; Do not pass through like first group of test, can get one group again and test.Its flame retardant resistance grade is divided into V-0, and V-1, and V-2 judge that by the listed index of table 1 wherein the flame retardant resistance of V-0 is best respectively, as all not in the listed indication range of table 1, then is judged to be NC (can not classify), and its flame retardant resistance is the poorest.
Table 1UL94 burning grade is judged index
| The sample burning behavior | V-0 | V-1 | V-2 |
| Sample number/root | 5 | 5 | 5 |
| Each sample is lighted number of times/inferior | 2 | 2 | 2 |
| Each sample is lighted the longest flaming combustion time/S of back individual sample | ＜10 | ＜30 | ＜30 |
| Light for the second time the longest flameless combustion time/S of back individual sample | ＜30 | ＜60 | ＜60 |
| 5 samples are lighted summation/S of back flaming combustion time for 10 times | ＜50 | ＜250 | ＜250 |
| Have or not molten drop and the molten drop absorbent cotton that whether ignites | Not | Not | Be |
| Whether be burned to retaining clip | Not | Not | Not |
Mechanical property
Tensile strength: the standard batten with injection moulding is good is measured by standard ISO 527, and rate of extension 5mm/min averages for 6 every group;
Flexural strength: the standard batten with injection moulding is good is measured by standard ISO 178, and crooked speed 2mm/min averages for 6 every group;
Gas vol
With the compsn pellet that cuts out after extruding, 150 ℃ place convection oven oven dry in 2 hours, after take by weighing 10g left and right sides sample and place the aluminum sample disc, put into 270 ℃ of convection oven and take out after 30 minutes, measure its gas vol (Outgas), and with following formula calculating:
Wherein, w
0For putting into the quality of compsn before the baking oven; w
1Quality for compsn behind the taking-up baking oven.Measuring 3 for every group averages.
Embodiment and Comparative Examples
Comparative Examples 1
Take by weighing thermoplastic polyester PBT, SULPHOSUCCINIC ACID ESTER PX200, organic secondary phosphine acid salt OP1240, anti-dripping agent A3800 and oxidation inhibitor IR1010 respectively in ratio shown in the table 2; Use the pre-mixing of mixed at high speed whipping appts even at normal temperatures; Compound is transported to quantitatively the TEX30 α parallel dual-screw extruding machine (JSW's system) from main hopper and melt extrudes; 250 ℃ of extrusion temperatures, rotating speed 200rpm, the tie rod after extruding are cut into the particle about length 3mm with dicing machine after tank cooling; This pellet is through 150 ℃ of forced air dryings after 4 hours; Be injection molded into the standard batten with NEX1000 injection moulding machine (a Japan day Seiko industry Co., Ltd. produces), carry out the mensuration of UL94, mechanical property and gas vol, its result sees table 2.
Comparative Examples 2
Take by weighing thermoplastic polyester PBT, polycarbonate IR2500 respectively in ratio shown in the table 2; SULPHOSUCCINIC ACID ESTER PX200, organic secondary phosphine acid salt OP 1240, anti-dripping agent A3800 and oxidation inhibitor IR1010; Use the pre-mixing of mixed at high speed whipping appts even at normal temperatures, compound is transported to quantitatively the TEX30 α parallel dual-screw extruding machine (JSW's system) from main hopper and melt extrudes 250 ℃ of extrusion temperatures; Rotating speed 200rpm; Tie rod after extruding is cut into the particle about length 3mm through tank cooling back with dicing machine, this pellet after 4 hours, is injection molded into standard batten with NEX1000 injection moulding machine (Japan's day Seiko is Co., Ltd.'s product already) through 150 ℃ of forced air dryings; Carry out the mensuration of UL94, mechanical property and gas vol, its result sees table 2.
Embodiment 1
Take by weighing thermoplastic polyester PBT, copolyesters TX-1000, SULPHOSUCCINIC ACID ESTER PX200, organic secondary phosphine acid salt OP 1240, anti-dripping agent A3800 and oxidation inhibitor IR1010 respectively in ratio shown in the table 2; Use the pre-mixing of mixed at high speed whipping appts even at normal temperatures; Compound is transported to quantitatively the TEX30 α parallel dual-screw extruding machine (JSW's system) from main hopper and melt extrudes; 250 ℃ of extrusion temperatures, rotating speed 200rpm, the tie rod after extruding are cut into the particle about length 3mm with dicing machine after tank cooling; This pellet is through 150 ℃ of forced air dryings after 4 hours; Be injection molded into the standard batten with NEX1000 injection moulding machine (a Japan day Seiko industry Co., Ltd. produces), carry out the mensuration of UL94, mechanical property and gas vol, its result sees table 2.
Embodiment 2
Take by weighing thermoplastic polyester PBT, polyarylester U-100, SULPHOSUCCINIC ACID ESTER PX200, organic secondary phosphine acid salt OP 1240, anti-dripping agent A3800 and oxidation inhibitor IR1010 respectively in ratio shown in the table 2; Use the pre-mixing of mixed at high speed whipping appts even at normal temperatures; Compound is transported to quantitatively the TEX30 α parallel dual-screw extruding machine (JSW's system) from main hopper and melt extrudes; 250 ℃ of extrusion temperatures, rotating speed 200rpm, the tie rod after extruding are cut into the particle about length 3mm with dicing machine after tank cooling; This pellet is through 150 ℃ of forced air dryings after 4 hours; Be injection molded into the standard batten with NEX1000 injection moulding machine (a Japan day Seiko industry Co., Ltd. produces), carry out the mensuration of UL94, mechanical property and gas vol, its result sees table 2.
Embodiment 3
Take by weighing thermoplastic polyester PBT, thermoplastic polyester PET, copolyesters TX-1000, melamine cyanurate MC4000, SULPHOSUCCINIC ACID ESTER PX200, organic secondary phosphine acid salt OP 1240, dripping agent A3800 and oxidation inhibitor IR1010 respectively in ratio shown in the table 2; Use the pre-mixing of mixed at high speed whipping appts even at normal temperatures; Compound is transported to quantitatively the TEX30 α parallel dual-screw extruding machine (JSW's system) from main hopper and melt extrudes; 250 ℃ of extrusion temperatures, rotating speed 200rpm, the tie rod after extruding are cut into the particle about length 3mm with dicing machine after tank cooling; This pellet is through 150 ℃ of forced air dryings after 4 hours; Be injection molded into the standard batten with NEX1000 injection moulding machine (a Japan day Seiko industry Co., Ltd. produces), carry out the mensuration of UL94, mechanical property and gas vol, its result sees table 2.
Embodiment 4
Take by weighing thermoplastic polyester PBT, thermoplastic polyester PET, thermoplastic polyester PTT, polyarylester U-100, SULPHOSUCCINIC ACID ESTER PX200, organic secondary phosphine acid salt OP 1240, poly cyanamid cyanurate MC4000, anti-dripping agent A3800 and oxidation inhibitor IR1010 respectively in ratio shown in the table 2; Use the pre-mixing of mixed at high speed whipping appts even at normal temperatures; Compound is from main hopper; Short glass fiber 3J948 is through the side feeding unit, and SULPHOSUCCINIC ACID ESTER RDP and BDP are transported to quantitatively in the TEX30 α parallel dual-screw extruding machine (JSW's system) with special-purpose liquid feeding device and melt extrude 250 ℃ of extrusion temperatures simultaneously; Rotating speed 200rpm; Tie rod after extruding is cut into the particle about length 3mm through tank cooling back with dicing machine, this pellet after 4 hours, is injection molded into standard batten with NEX1000 injection moulding machine (Japan's day Seiko is Co., Ltd.'s product already) through 150 ℃ of forced air dryings; Carry out the mensuration of UL94, mechanical property and gas vol, its result sees table 2.
Embodiment 5
Take by weighing thermoplastic polyester PET, polyarylester U-100, copolyesters TX-1000, phosphide PX200, organic secondary phosphine acid salt OP 950, anti-dripping agent A3800 and oxidation inhibitor IR1010 respectively in ratio shown in the table 2; Use the pre-mixing of mixed at high speed whipping appts even at normal temperatures; Compound is from main hopper, and short glass fiber 3J948 is transported to quantitatively in the TEX30 α parallel dual-screw extruding machine (JSW's system) through the side feeding unit and melt extrudes 250 ℃ of extrusion temperatures; Rotating speed 200rpm; Tie rod after extruding is cut into the particle about length 3mm through tank cooling back with dicing machine, this pellet after 4 hours, is injection molded into standard batten with NEX1000 injection moulding machine (Japan's day Seiko is Co., Ltd.'s product already) through 150 ℃ of forced air dryings; Carry out the mensuration of UL94, mechanical property and gas vol, its result sees table 2.
Embodiment 6
Take by weighing thermoplastic polyester PBT, copolyesters TX-1000, organic secondary phosphine acid salt OP1240, melamine cyanurate MC4000, mica, anti-dripping agent A3800 and oxidation inhibitor IR1010 respectively in ratio shown in the table 2; Use the pre-mixing of mixed at high speed whipping appts even at normal temperatures; Compound is from main hopper; Short glass fiber 3J948 is through the side feeding unit, and SULPHOSUCCINIC ACID ESTER RDP and BDP are transported to quantitatively in the TEX30 α parallel dual-screw extruding machine (JSW's system) with special-purpose liquid feeding device and melt extrude 250 ℃ of extrusion temperatures simultaneously; Rotating speed 200rpm; Tie rod after extruding is cut into the particle about length 3mm through tank cooling back with dicing machine, this pellet after 4 hours, is injection molded into standard batten with NEX1000 injection moulding machine (Japan's day Seiko is Co., Ltd.'s product already) through 150 ℃ of forced air dryings; Carry out the mensuration of UL94, mechanical property and gas vol, its result sees table 2.
Embodiment 7
Take by weighing thermoplastic polyester PET, thermoplastic polyester PTT, copolyesters TX-1000, SULPHOSUCCINIC ACID ESTER PX200, organic secondary phosphine acid salt OP 1240, organic secondary phosphine acid salt OP 950, melamine cyanurate MC4000 respectively in ratio shown in the table 2; Lime carbonate, anti-dripping agent A3800 and oxidation inhibitor IR1010; Use the pre-mixing of mixed at high speed whipping appts even at normal temperatures; Compound is from main hopper, and short glass fiber 3J948 is transported to quantitatively in the TEX30 α parallel dual-screw extruding machine (JSW's system) through the side feeding unit and melt extrudes 250 ℃ of extrusion temperatures; Rotating speed 200rpm; Tie rod after extruding is cut into the particle about length 3mm through tank cooling back with dicing machine, this pellet after 4 hours, is injection molded into standard batten with NEX1000 injection moulding machine (Japan's day Seiko is Co., Ltd.'s product already) through 150 ℃ of forced air dryings; Carry out the mensuration of UL94, mechanical property and gas vol, its result sees table 2.
Embodiment 8
Take by weighing thermoplastic polyester PET, thermoplastic polyester PTT, copolyesters TX-1000, SULPHOSUCCINIC ACID ESTER PX200, organic secondary phosphine acid salt OP 950, lime carbonate, mica, anti-dripping agent A3800 and oxidation inhibitor IR1010 respectively in ratio shown in the table 2; Use the pre-mixing of mixed at high speed whipping appts even at normal temperatures; Compound is from main hopper; Short glass fiber 3J948 is through the side feeding unit, and SULPHOSUCCINIC ACID ESTER BDP is transported to quantitatively in the TEX30 α parallel dual-screw extruding machine (JSW's system) with special-purpose liquid feeding device and melt extrudes 250 ℃ of extrusion temperatures simultaneously; Rotating speed 200rpm; Tie rod after extruding is cut into the particle about length 3mm through tank cooling back with dicing machine, this pellet after 4 hours, is injection molded into standard batten with NEX1000 injection moulding machine (Japan's day Seiko is Co., Ltd.'s product already) through 150 ℃ of forced air dryings; Carry out the mensuration of UL94, mechanical property and gas vol, its result sees table 2.
The proportioning and the performance thereof of the low gas vol halogen-free flame-retardant thermoplastic polyester compsn of table 2
Claims (9)
1. one kind low gas vol halogen-free flame-retardant thermoplastic polyester compsn is characterized in that:
Said composition mainly by
(A) at least a polyalkylene terephthalates of 25-65 weight part,
(B) at least a copolyesters with ad hoc structure of 1-15 weight part,
(C) at least a aromatic phosphoric ester with structure shown in the formula (I) of 1-30 weight part,
(D) at least a diphosphinic acid salt that is selected from the phosphinates of the structure shown in (II) that has formula and/or has a structure shown in (III) of 1-30 weight part is formed;
The copolyesters with ad hoc structure described in above-mentioned (B) is to be selected from one or more diprotic acid and the product that (b) is selected from one or more divalent alcohol copolyreaction shown in formula (b1), formula (b2), formula (b3), formula (b4) and/or the formula (b5) in terephthalic acid or the m-phthalic acid by (a):
R in the formula
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8, R
9, R
10, R
11, R
12, R
13, R
14, R
15, R
16, R
17And R
18Be the alkyl of Wasserstoffatoms or C1-C5 independently respectively;
The structural formula of (I) is described in above-mentioned (C):
Ar1, Ar2, Ar3 and Ar4 be not respectively independently for replacing or substituted not halogen-containing aromatic base n in the formula
1Be the integer of 0-5, Y is the not halogen-containing arylidene shown in formula (c1), formula (c2) or the formula (c3):
R wherein
19, R
20, R
21, R
22, R
23, R
24, R
25And R
26Be the alkyl of Wasserstoffatoms or C1-C5 independently respectively, Z representes direct key, O, S, SO
2, CH
2Or C (CH
3)
2
(II) and structural formula (III) are respectively described in above-mentioned (D):
R in the formula
27, R
28, R
29And R
31For identical or different, and be alkyl and/or the aryl of hydrogen, straight chain or the C1-C6 that has side chain; R
30Be the alkylidene group of C1-C10 straight or branched, arylidene, alkyl arylene and/or the aryl alkylene of C6-C10; M, N are identical or different, and are earth alkali metal class, basic metal class, aluminium, zinc, titanium, zirconium, silicon, tin and/or a kind of protonated nitrogen base; M, m ' are identical or different, and are the integer of 1-4; n
2It is the integer of 1-4; X is the integer of 1-4.
2. low gas vol halogen-free flame-retardant thermoplastic polyester compsn according to claim 1 is characterized in that: said composition also contains (E) 0-35 weight part melamine cyanurate.
3. low gas vol halogen-free flame-retardant thermoplastic polyester compsn according to claim 1 and 2 is characterized in that: said composition also contains (F) 0-40 weight part fortifying fibre.
4. low gas vol halogen-free flame-retardant thermoplastic polyester compsn according to claim 1 is characterized in that: described component (A) polyalkylene terephthalates is selected from one or more in polyethylene terephthalate, PTT and/or the polybutylene terephthalate.
5. low gas vol halogen-free flame-retardant thermoplastic polyester compsn according to claim 1 is characterized in that: the ratio of the gross weight umber of the gross weight umber of said component (C) and component (D) is 0.1～15.
6. low gas vol halogen-free flame-retardant thermoplastic polyester compsn according to claim 1; It is characterized in that: the copolyesters that described component (B) has ad hoc structure is (a) terephthalic acid and the product that (b) is selected from one or more divalent alcohol copolyreaction of structure shown in formula (b1), formula (b3) and/or the formula (b5), and wherein (b1), (b3) and structure (b5) are respectively:
R in the formula
1, R
2, R
5, R
6, R
7, R
8, R
15, R
16, R
17And R
18Be the alkyl of Wasserstoffatoms or C1-C5 independently respectively.
7. according to claim 1 or 5 described low gas vol halogen-free flame-retardant thermoplastic polyester compsns; It is characterized in that: said component (C) is selected from one or more in dihydroxyphenyl propane two (diphenyl phosphoester), Resorcinol two (diphenyl phosphoester), Resorcinol two [two (2, the 6-3,5-dimethylphenyl) SULPHOSUCCINIC ACID ESTER] and/or the Resorcinol two (diphenylphosphine acid phenenyl ester).
8. according to claim 1 or 5 described low gas vol halogen-free flame-retardant thermoplastic polyester compsns, it is characterized in that: said component (D) is selected from one or more in diethylammonium phospho acid calcium, diethylammonium phospho acid zinc and/or the diethylammonium phospho acid aluminium.
9. low gas vol halogen-free flame-retardant thermoplastic polyester compsn according to claim 3 is characterized in that: described component (E) fortifying fibre is selected from one or more of spun glass, thomel, basalt fibre or aromatic polyamide fibre.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103102656A (en) * | 2013-01-31 | 2013-05-15 | 广东银禧科技股份有限公司 | Low-cost, high-heat-resistant, halogen-free, flame-retardant and glass fiber-reinforced PBT (polybutylece terephthalate) composition and preparation method thereof |
| CN103289338A (en) * | 2013-06-24 | 2013-09-11 | 苏州新区佳合塑胶有限公司 | Halogen-free flame-retardant PBT composite material with high mechanical properties |
| CN103450642A (en) * | 2013-08-07 | 2013-12-18 | 上海日之升新技术发展有限公司 | High-strength carbon-fiber-reinforced halogen-free flame-retardant PBT (polybutylene terephthalate) composite material and preparation method thereof |
| CN104693692A (en) * | 2013-12-05 | 2015-06-10 | 杜邦公司 | Flame-resistance polytrimethylene terephthalate composition and product thereof |
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2011
- 2011-02-14 CN CN201110041944XA patent/CN102634170A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103102656A (en) * | 2013-01-31 | 2013-05-15 | 广东银禧科技股份有限公司 | Low-cost, high-heat-resistant, halogen-free, flame-retardant and glass fiber-reinforced PBT (polybutylece terephthalate) composition and preparation method thereof |
| CN103102656B (en) * | 2013-01-31 | 2015-08-12 | 广东银禧科技股份有限公司 | Low cost high heat-resistant halogen-free flame-retardant fiber glass reinforced PBT composition and method of making the same |
| CN103289338A (en) * | 2013-06-24 | 2013-09-11 | 苏州新区佳合塑胶有限公司 | Halogen-free flame-retardant PBT composite material with high mechanical properties |
| CN103450642A (en) * | 2013-08-07 | 2013-12-18 | 上海日之升新技术发展有限公司 | High-strength carbon-fiber-reinforced halogen-free flame-retardant PBT (polybutylene terephthalate) composite material and preparation method thereof |
| CN104693692A (en) * | 2013-12-05 | 2015-06-10 | 杜邦公司 | Flame-resistance polytrimethylene terephthalate composition and product thereof |
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Application publication date: 20120815 |