WO2016008074A1 - 无卤阻燃高温尼龙 - Google Patents
无卤阻燃高温尼龙 Download PDFInfo
- Publication number
- WO2016008074A1 WO2016008074A1 PCT/CN2014/082158 CN2014082158W WO2016008074A1 WO 2016008074 A1 WO2016008074 A1 WO 2016008074A1 CN 2014082158 W CN2014082158 W CN 2014082158W WO 2016008074 A1 WO2016008074 A1 WO 2016008074A1
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- WIPO (PCT)
- Prior art keywords
- group
- halogen
- acid
- aromatic
- free flame
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- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 125000001977 isobenzofuranyl group Chemical group C=1(OC=C2C=CC=CC12)* 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000005956 isoquinolyl group Chemical group 0.000 description 1
- 125000000842 isoxazolyl group Chemical group 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- FWQWBCXBNYKFCJ-UHFFFAOYSA-N methylcyclohexane Chemical compound C[C-]1CCCCC1 FWQWBCXBNYKFCJ-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- DIOQZVSQGTUSAI-UHFFFAOYSA-N n-butylhexane Natural products CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 1
- 125000004998 naphthylethyl group Chemical group C1(=CC=CC2=CC=CC=C12)CC* 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 229920006119 nylon 10T Polymers 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920006115 poly(dodecamethylene terephthalamide) Polymers 0.000 description 1
- 229920006139 poly(hexamethylene adipamide-co-hexamethylene terephthalamide) Polymers 0.000 description 1
- 229920006117 poly(hexamethylene terephthalamide)-co- polycaprolactam Polymers 0.000 description 1
- 229920006128 poly(nonamethylene terephthalamide) Polymers 0.000 description 1
- 229920000470 poly(p-phenylene terephthalate) polymer Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- KRIOVPPHQSLHCZ-UHFFFAOYSA-N propiophenone Chemical compound CCC(=O)C1=CC=CC=C1 KRIOVPPHQSLHCZ-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 125000002294 quinazolinyl group Chemical group N1=C(N=CC2=CC=CC=C12)* 0.000 description 1
- 125000005493 quinolyl group Chemical group 0.000 description 1
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000012783 reinforcing fiber Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
Definitions
- the present invention relates to a halogen-free flame retardant semi-aromatic high temperature nylon. Background technique
- SMT surface mount components
- SMD surface mount components
- Semi-aromatic high temperature nylon is thus obtained in SMD.
- the general semi-aromatic high-temperature nylon is flammable, it is necessary to add a flame retardant in actual use to meet the requirements of fire safety.
- semi-aromatic high-temperature nylons usually use a bromine-based flame retardant to achieve a flame retardant effect.
- bromine-based flame retardants burn, they generate strong irritating hydrogen bromide gas, smoke, and even some strong carcinogenic substances, which limits the use of brominated flame retardants.
- the EU has also enacted laws and regulations such as REACH and RoHS to limit the use of certain brominated flame retardants, so the industry has turned to halogen-free flame retardants.
- diterpene phosphinates especially aluminum diethylphosphinate
- diterpene phosphinates are used as flame retardants for high temperature nylons, see U.S. Patent No. 7,294,661; U.S. Patent Application Nos. US200806897K US20100261818, US20120029124, US2013049040 and US20140011925.
- the diterpene phosphinates are corrosive and their corrosivity is particularly severe at high temperatures.
- the aluminum bisphosphonate is solid at the processing temperature of high temperature nylon, which causes a decrease in the flow properties of the product and affects the production of complex electronic components.
- Phosphonates especially cyclic phosphonates, have also been reported as flame retardants.
- WO2010135398 reports a derivative of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) which contains two phosphorus centers (DiDOPO) in one molecule and has good Thermal stability and flame retardancy, but structurally limited to the vinyl bridge chain (-CH 2 CH 2 -) between the two phosphorus centers.
- DOPO 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide
- WO2012064703 describes DiDOPO with different bridging chains as flame retardants for epoxy resins, and this patent application does not include aromatic substituted vinyl bridges.
- JPH11-106619 reports a derivative of DOPO, DiDOPO, which does not mention an aromatic-substituted vinyl bridge and is limited to polyester fibers.
- Japanese laid-open patent application JP2001270993 describes a derivative of DOPO, DiDOPO, which has a DiDOPO bridge chain longer than a vinyl bridge chain, and the bridge chain is too long to cause an increase in the plasticizing property of DiDOPO, causing a decrease in the heat distortion temperature of the engineering plastic article.
- the substituent on the DiDOPO alkenylene bridge of the patent application is a hydroxyl group or a decyloxy group.
- the introduction of hydroxyl groups reduces the thermal stability of the flame retardant and is detrimental to the processing of engineering plastics.
- the introduction of a decyloxy group increases the oxidizing properties and leads to early degradation of the polymer material.
- This patent application does not mention an aromatic substituted vinyl bridge.
- the present application provides a halogen-free flame retardant high temperature nylon based on a DOPO derivative.
- the DOPO The derivative has good flame retardant effect, good thermal stability and chemical stability, and can overcome the shortcomings of the chemical resistance of the existing DiDOPO flame retardant or the plasticizer without reducing the high-temperature nylon processing fluidity.
- the high temperature nylon fire test prepared by using it as a flame retardant has a UL94 V-0 rating of 0.8 mm. Summary of the invention
- the present application provides a halogen-free flame-retardant high-temperature nylon characterized by containing a polyamide and a compound A; the compound A has a chemical structural formula as shown in the formula (1):
- Ar is optionally selected from a heteroaryl group of C3 C18 or an aryl group of C6 C18;
- R 3 , , R 5 and R 6 are independently selected from hydrogen, C1-C18 indenyl, C3 C18 heteroaryl, C6-C18 aryl;
- n, k and p are independently selected from 0, 1, 2, 3, 4;
- Any hydrogen atom on the aryl or heteroaryl aromatic ring may be independently substituted with any C1-C18 fluorenyl group.
- R 2 is a fluorenyl group
- the polyamide is selected from the group consisting of a semi-aromatic polyamide, a mixture of a semi-aromatic polyamide and an aliphatic polyamide, a copolymer of a semi-aromatic polyamide and an aliphatic polyamide.
- the aryl group and the heteroaryl group are groups formed by losing any one of the hydrogen atoms in the aromatic ring in the aromatic compound molecule.
- the group formed is an aryl group; when the aromatic ring contains a hetero atom such as N, 0, S or the like, the group formed is a heteroaryl group.
- the aromatic compound which forms an aryl group or a heteroaryl group may have a substituent or a substituent on the aromatic ring, and a typical substituent such as a fluorenyl group, a carboxyl group, a hydroxyl group, a halogenated group or the like.
- the heteroaryl group of C3 C18 is a group formed by an aromatic compound molecule having a heterocyclic ring having 3 to 18 carbon atoms and having an arbitrary hydrogen atom lost on the aromatic ring.
- C3-C18 means that the number of carbon atoms in the heterocyclic aromatic ring in the heteroaryl group is from 3 to 18.
- the heterocyclic aromatic ring is an aromatic ring containing a hetero atom such as N, 0 or S.
- An aromatic compound containing a heterocyclic aromatic ring which comprises a fused ring aromatic ring compound formed by a heterocyclic ring and a benzene ring, such as benzofuran, a group formed by the loss of any one of the hydrogen atoms on the benzene ring or the furan ring, all of which are heteroaryl base.
- the aryl group of C6 C18 is a group formed by an aromatic compound having an aromatic ring having 6 to 18 carbon atoms and containing no hetero atom in the aromatic ring, and having any hydrogen atom lost on the aromatic ring.
- C6 C18 means that the number of carbon atoms in the aromatic ring containing no hetero atom in the aryl group is 6-18.
- An aromatic compound which does not contain a hetero atom aromatic ring means that a conjugated aromatic ring system does not contain a hetero atom such as N, 0 or S.
- the fluorenyl group of C1 C18 is a linear fluorenyl group having 1 to 18 carbon atoms, a branched fluorenyl group having 1 to 18 carbon atoms or a fluorenyl group having an aromatic ring.
- the sulfhydryl group containing an aromatic ring is a aryl group An aromatic compound having a mercapto substituent present on the aromatic ring, a group formed by losing any hydrogen atom on the indenyl group in the molecule.
- the fluorenyl group is a saturated hydrocarbon group, that is, a hydrocarbon group in which a hydrazine hydrocarbon molecule loses one hydrogen atom, and contains a linear fluorenyl group and a branched fluorenyl group.
- the thiol group is selected from the group consisting of methyl, ethyl, propyl, butyl, isopropyl, t-butyl, isobutyl, pentyl and hexyl.
- the aromatic ring may be a monocyclic aromatic ring, a polycyclic aromatic ring or a fused ring aromatic ring.
- the monocyclic aromatic ring may be a benzene ring or a five- or six-membered heterocyclic ring containing a hetero atom such as N, 0 or S.
- the polycyclic aromatic ring which contains a plurality of benzene rings and/or heterocyclic rings, and between the benzene ring and the benzene ring, between the benzene ring and the hetero ring, and between the hetero ring and the hetero ring, does not share a carbon atom, such as Benzene ring.
- the fused ring aromatic ring contains a plurality of benzene rings and/or heterocyclic rings, and a common carbon atom exists between the benzene ring and the benzene ring, between the benzene ring and the hetero ring, and between the hetero ring and the hetero ring.
- common heteroaryl groups are furyl, benzofuranyl, isobenzofuranyl, pyrrolyl, decyl, isodecyl, thienyl, benzo[b]thienyl, benzene.
- Common aryl groups are phenyl, naphthyl, anthracenyl, phenanthryl.
- the heteroaryl group is selected from a furyl group, a benzofuranyl group; the aryl group is selected from the group consisting of phenyl, naphthyl, anthracenyl, fluorenyl, methylphenyl, ethylphenyl, propyl Phenyl, butylphenyl, dimethylphenyl, isopropylphenyl, isobutylphenyl or tert-butylphenyl.
- the structural formula of the compound A is selected from one of the formula (2), the formula (3), the formula (4), the formula (5), the formula (6), and the formula (7).
- the present application also provides a method for preparing the compound A, which comprises reacting an aryl ketone and a DOPO compound under the action of an acidic catalyst;
- aryl ketone is one or more selected from the group consisting of compounds having the formula (8);
- the DOPO-based compound is selected from one or more of the compounds having the formula (9);
- Ar is optionally a heteroaryl group selected from C3 C18 or an aryl group of C6 C18;
- R nR 2 is independently selected from hydrogen, a C1 C18 indenyl group, a C3 C18 heteroaryl group, and a C6 C18 aromatic group.
- q and j are independently selected from 0, 1, 2, 3, 4;
- Any hydrogen atom on the aryl or heteroaryl aromatic ring may be independently substituted with any C1-C18 alkyl group.
- the aryl ketone is selected from the group consisting of acetophenone, 2-naphthylethyl ketone, furan ethyl ketone, 1-naphthyl ethyl ketone, propiophenone, acetophenone, acetophenone, and phenyl benzyl ketone.
- acetophenone 2-naphthylethyl ketone
- furan ethyl ketone furan ethyl ketone
- 1-naphthyl ethyl ketone propiophenone
- acetophenone acetophenone
- acetophenone acetophenone
- phenyl benzyl ketone phenyl benzyl ketone
- the acidic catalyst contains hydrogen chloride and/or hydrogen bromide, or contains a substance capable of generating hydrogen chloride and/or hydrogen bromide in the presence of a hydroxyl group, or contains hydrogen chloride and/or bromine in the presence of water. Hydrogen substance.
- the acidic catalyst contains any one or a mixture of any of hydrogen chloride, hydrogen bromide, phosphorus trichloride, and phosphorus oxychloride.
- the reaction temperature is 0 to 250 ° C, and a further preferred reaction temperature is 80 to 200 ° (: The temperature is lower than 0 ° C, the reaction rate is slow; and the temperature is higher than 250 ° C, and the by-products are greatly increased.
- the reaction can be carried out under normal pressure, positive pressure or under negative pressure.
- the number of moles of the catalyst is based on the number of moles of chlorine and/or bromine contained in the catalyst.
- the DOPO-based compound, the aryl ketone and the acidic catalyst may be mixed in any order, or all or part of any two may be mixed first, and then the remaining portion and the third component may be added.
- the DOPO and the aryl ketone are first mixed, and then the acidic catalyst is slowly added dropwise.
- reaction system contains an inert solvent.
- the inert solvent is selected from one or more selected from the group consisting of cyclohexanone, methylcyclohexanide, toluene, benzene, xylene, hexanthene, gadolinium, octyl, cumene, t-butylbenzene.
- cyclohexanone methylcyclohexanide
- toluene benzene
- benzene xylene
- hexanthene gadolinium
- octyl cumene
- t-butylbenzene t-butylbenzene
- DOPO chemical name is 9,10-dihydro-9-oxa-10-phosphaphenanthrene- 10-oxide.
- the DOPO-like compounds described herein comprise DOPO and DOPO derivatives.
- a DOPO derivative refers to a benzene ring in the chemical structural formula of DOPO, and a hydrogen atom is substituted by another substituent, often The substituents which may be seen are methyl, ethyl, isopropyl, t-butyl, chloro and the like.
- polyamide is also called nylon or nylon, and is contained in its structural unit.
- Polyamides are generally classified into aliphatic polyamides, aromatic polyamides, and semi-aromatic polyamides depending on the components of their main chains.
- the semi-aromatic polyamide means that at least one of the monomers in the synthetic monomer contains an aromatic group.
- the semi-aromatic polyamide may be prepared from any one or more aromatic dicarboxylic acids and any one or more aliphatic diamines, or may be any one or several aromatic binary
- the amine is prepared with any one or more aliphatic dicarboxylic acids.
- One or any of any one selected from the group consisting of dicarboxylic acids, diamines, lactams and amino acids may also be added to the system to prepare a polyamide copolymer having a corresponding property.
- the added dicarboxylic acid is an aromatic dicarboxylic acid and/or an aliphatic dicarboxylic acid;
- the added diamine is an aromatic diamine and/or an aliphatic diamine;
- the added lactam may be fat Family or aromatic lactam.
- the added amino acid can be an aromatic or aliphatic amino acid.
- the semi-aromatic polyamide is prepared from an aliphatic diamine, an aromatic dicarboxylic acid, and an aliphatic dicarboxylic acid.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
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Abstract
本申请涉及一种无卤阻燃高温尼龙,其特征在于,含有聚酰胺和DOPO 衍生物。该无卤阻燃高温尼龙0.8毫米燃烧测试达到UL94V-0级别,具有良好的热稳定性、化学稳定性和机械性能,以其为主要原料制作的表面贴装元件(SMD),满足表面贴装过程(SMT)中高温红外回流炉焊接工艺的使用要求。
Description
无卤阻燃髙温尼龙
技术领域
本发明涉及无卤阻燃半芳香族高温尼龙。 背景技术
电子电器的小型化和多功能化, 促使制造业加速采用表面贴装技术
( SMT)来实现电子元器件的高密度化。 由于 SMT过程需要使用高温红外 回流炉来悍接表面贴装元件 (SMD), 要求 SMD的材料具有杰出的热稳定 性、化学稳定性和机械性能, 半芳香族类高温尼龙由此在 SMD中得到极大 的应用。 但由于一般的半芳香族类高温尼龙具有可燃性, 因此在实际使用 时需要添加阻燃剂, 以达到防火安全的要求。 传统上, 半芳香族类高温尼 龙通常采用溴系阻燃剂, 实现阻燃效果。 但溴系阻燃剂在燃烧时, 会产生 强烈刺激性的溴化氢气体、 浓烟、 甚至一些强烈致癌性物质, 使得溴系阻 燃剂的使用受到了限制。欧盟更是制定了法律和法规譬如 REACH 和 RoHS, 限制某些溴系阻燃剂的使用, 因此工业界开始转向无卤阻燃剂。
在半芳香族类高温尼龙这方面, 寻找合适的无卤阻燃剂存在着巨大的挑 战。 半芳香族类高温尼龙的熔点非常高 (超过 300°C ), 加工温度常常需要 在 310-350°C之间, 这导致一般的无卤阻燃剂譬如聚磷酸胺等由于缺乏足够 的热稳定性而不能满足其加工要求, 因此目前该领域的研究主要集中在发 展具有高度热稳定性的无卤阻燃剂上。
由于含磷-碳键的化合物具有良好的热稳定性和化学稳定性,膦酸盐类化
合物在无卤阻燃方面得到了应用。 譬如二垸基次膦酸盐特别是二乙基次膦 酸铝被用作高温尼龙的阻燃剂, 见美国专利 US7294661 ; 美国专利申请 US200806897K US20100261818, US20120029124, US2013049040和 US20140011925。但二垸基次膦酸盐具有腐蚀性, 它们的腐蚀性在高温情况 下尤其严重。 另外二垸基次膦酸铝在高温尼龙的加工温度下是固体, 会引 起制品流动性能的降低, 影响复杂电子元器件的制作。
膦酸酯类特别是环状膦酸酯类也被报道作为阻燃剂。 WO2010135398报 道了 9, 10-二氢 -9-氧杂 -10-磷杂菲 -10-氧化物 (DOPO) 的衍生物, 该衍生 物一个分子中含有 2个磷中心 (DiDOPO), 具有良好的热稳定性和阻燃性, 但结构上仅限于 2个磷中心之间的乙烯基桥链(-CH2CH2-)。 WO2012064703 描述了具有不同桥链的 DiDOPO作为环氧树脂的阻燃剂, 该专利申请不包 括芳香基取代的乙烯基桥链。
日本公开专利申请 JPH11-106619报道了 DOPO的衍生物 DiDOPO, 该 专利申请没有提到芳香基取代的乙烯基桥链, 且仅限应用于聚酯纤维。
日本公开专利申请 JP2001270993描述了 DOPO的衍生物 DiDOPO, 该 专利申请描述的 DiDOPO桥链长于乙烯基桥链, 桥链太长导致 DiDOPO的 塑化性能增加, 引起工程塑料制品热变形温度的下降。 并且该专利申请描 述的 DiDOPO亚烯基桥链上的取代基是羟基或垸氧基。 羟基的引入降低了 阻燃剂的热稳定性, 对工程塑料的加工不利。 垸氧基的引入则增加了被氧 化性能, 会导致高分子材料的提早降解。 该专利申请没有提到芳香基取代 的乙烯基桥链。
本申请提供了一种基于 DOPO衍生物的无卤阻燃高温尼龙。 该 DOPO
衍生物阻燃效果好, 具有良好的热稳定性和化学稳定性, 能够在不降低高 温尼龙加工流动性的同时, 克服已有 DiDOPO阻燃剂的耐化学性不足或者 塑化性强的缺点。 以其为阻燃剂制备的高温尼龙燃烧测试 0.8毫米达到 UL94 V-0级别。 发明内容
为解决上述技术问题, 本申请提供了一种无卤阻燃高温尼龙, 其特征在 于, 含有聚酰胺和化合物 A; 化合物 A具有如式 (1)所示的化学结构式:
Ar任选自 C3 C18的杂芳基或 C6 C18的芳基;
和 独立地任选自氢、 C1 C18的垸基、 C3 C18的杂芳基、 C6 C18 的芳基;
R3, , R5和 R6独立地任选自氢、 C1-C18的垸基、 C3 C18的杂芳基、 C6-C18的芳基;
m, n, k和 p独立地任选自 0, 1, 2, 3, 4;
所述芳基或杂芳基芳香环上的任意氢原子可以独立被任意 C1-C18的垸 基取代。
优选地, 和1 2均为氢, m=n=k=p=0。
优选地, 为氢, R2为芳基, m=n=k=p=0。
优选地, 为氢, R2为垸基, m=n=k=p=0。
优选地, 所述聚酰胺任选自半芳香族聚酰胺、 半芳香族聚酰胺与脂肪族 聚酰胺的混合物、 半芳香族聚酰胺与脂肪族聚酰胺的共聚物。
本申请中, 所述芳基和杂芳基为芳香族化合物分子中失去芳香环上任意 一个氢原子后形成的基团。 当芳香环上不包含 N、 0、 S等杂原子时, 形成 的基团为芳基; 当芳香环上包含N、 0、 S等杂原子时, 形成的基团为杂芳 基。 形成芳基或杂芳基的芳香族化合物, 芳香环上可以没有取代基也可以 有取代基, 典型的取代基如垸基、 羧基、 羟基、 卤代基等。
本申请中, 所述 C3 C18的杂芳基是含有碳原子数为 3~18杂环芳香环 的芳香族化合物分子中, 芳香环上失去任意一个氢原子后形成的基团。 C3-C18 指的是杂芳基中杂环芳香环上的碳原子数为 3~18。 杂环芳香环为 含有 N、 0、 S等杂原子的芳香环。 含有杂环芳香环的芳香族化合物, 包含 杂环与苯环形成的稠环芳香环化合物, 如苯并呋喃, 其苯环或者呋喃环上 失去任意一个氢原子形成的基团, 均为杂芳基。
本申请中, 所述 C6 C18的芳基是芳香环碳原子数为 6~18且芳香环上 不含有杂原子的芳香族化合物分子中, 芳香环上失去任意一个氢原子后形 成的基团。 C6 C18指的是芳基中不含杂原子的芳香环上的碳原子数为 6~18。 不含有杂原子芳香环的芳香族化合物,指共轭的芳香环体系中,不包含 N、 0、 S等杂原子。
所述 C1 C18的垸基为碳原子数为 1~18的直链垸基、 碳原子数为 1~18 的带有支链的垸基或者含有芳香环的垸基。 所述含有芳香环的垸基, 为芳
香环上存在垸基取代基的芳香族化合物, 分子中失去垸基上任意一个氢原 子后形成的基团。
优选地,所述垸基为饱和烃基,即垸烃分子失去一个氢原子而成的烃基, 包含直链垸基和带有支链的垸基。 进一步优选的, 所述垸基任选自甲基、 乙基、 丙基、 丁基、 异丙基、 叔丁基、 异丁基、 戊基和己基。
本申请中,所述芳香环可以为单环芳香环、多环芳香环或者稠环芳香环。 其中, 所述单环芳香环可以为苯环, 也可以为含有 N、 0、 S等杂原子的五 元或者六元杂环。 所述多环芳香环, 含有多个苯环和 /或杂环, 且苯环与苯 环之间、 苯环与杂环之间、 杂环与杂环之间, 不共用碳原子, 如联苯环。 所述稠环芳香环, 含有多个苯环和 /或杂环, 且苯环与苯环之间、 苯环与杂 环之间、 杂环与杂环之间, 存在共用的碳原子, 如萘环、 苯并呋喃环等。
根据本领域公知常识, 常见的杂芳基有呋喃基、 苯并呋喃基、 异苯并呋 喃基、 吡咯基、 吲哚基、 异吲哚基、 噻吩基、 苯并 [b]噻吩基、 苯并 [c]噻吩 基、 咪唑基、 苯并咪唑基、 嘌呤基、 吡唑基、 吲唑基、 恶唑基、 苯并恶唑 基、 异恶唑基、 苯并异恶唑基、 噻唑基、 苯并噻唑基、 吡啶基、 喹啉基、 异喹啉基、 吡嗪基、 喹喔啉基、 吖啶基、 嘧啶基、 喹唑啉基、 哒嗪基、 酞 嗪基和噌啉基。 常见的芳基有苯基、 萘基、 蒽基、 菲基。
优选地,所述杂芳基任选自呋喃基、苯并呋喃基;所述芳基任选自苯基、 萘基、 茚基、 芴基、 甲基苯基、 乙基苯基、 丙基苯基、 丁基苯基、 二甲基 苯基、 异丙基苯基、 异丁基苯基或叔丁基苯基。
典型地,所述化合物 A的结构式任选自式(2)、式(3 )、式(4 )、式(5 )、 式 (6)、 式 (7 ) 中的一种,
所述 DOPO类化合物, 任选自具有式 (9) 结构式的化合物中的一种或 几种;
式(8) 中, Ar任选自 C3 C18的杂芳基或 C6 C18的芳基; R nR2独 立地任选自氢、 C1 C18的垸基、 C3 C18的杂芳基、 C6 C18的芳基; 式(9) 中, 17和 独立地任选自氢、 C1~C18的垸基、 C3~C18的杂芳 基、 C6-C18的芳基;
q和 j独立地任选自 0, 1, 2, 3, 4;
所述芳基或杂芳基芳香环上的任意氢原子可以独立被任意 C1-C18的烧 基取代。
优选地, 所述芳基酮任选自苯乙酮、 2-萘乙酮、 呋喃乙酮、 1-萘乙酮、 苯丙酮、 茚乙酮、 芴乙酮、 和苯基苄基酮中的一种或多种。
优选地, 所述酸性催化剂含有氯化氢和 /或溴化氢, 或者含有在羟基存在 条件下能够产生氯化氢和 /或溴化氢的物质, 或者含有在水存在条件下能够 产生氯化氢和 /或溴化氢的物质。
优选地, 所述酸性催化剂含有氯化氢、 溴化氢、 三氯化磷、 三氯氧磷中 的任意一种或任意几种的混合物。
优选地, 反应温度为 0~250°C, 进一步优选的反应温度为 80~200° (:。 温 度低于 0°C, 反应速度缓慢; 温度高于 250°C, 副产物大量增多。
反应可以在常压、 正压或负压条件下进行。
优选地, 所述 DOPO类化合物、 芳基酮和酸性催化剂的摩尔比为 DOPO 类化合物:芳基酮:酸性催化剂 =5~1 :1:0.02~10;进一步优选的范围为 DOPO 类化合物: 芳基酮: 酸性催化剂的摩尔比 =3~1 :1:0.1~10; 更进一步优选的 范围为 DOPO类化合物: 芳基酮: 酸性催化剂的摩尔比 =2.5~1: 1:0.1~0.9; 其中, 催化剂的摩尔数以催化剂中所含氯元素和 /或溴元素的摩尔数计。
其中, DOPO类化合物、 芳基酮和酸性催化剂可以以任意次序混合, 也 可以先混合任意两个的全部或部分, 然后加入剩余部分和第三组分。 优选 地, 先混合 DOPO和芳基酮, 然后慢慢滴加酸性催化剂。
可选择地, 反应体系中含有惰性溶剂。
优选地,所述惰性溶剂任选自环己垸、 甲基环己垸、 甲苯、苯、二甲苯、 己垸、 庚垸、 辛垸、 异丙苯、 叔丁基苯中的一种或几种。
DOPO类化合物和芳基酮的反应机理如下:
DOPO类化合物进攻芳香基酮的羰基, 产生 α-ΟΗ膦酸酯, 羟基随即被 亲核的氯化氢或溴化氢取代产生水和 a-氯代或溴代膦酸酯, 后者通过消除 反应重新生成氯化氢或溴化氢以及含 C=C的取代乙烯基膦酸酯, 随后第二 分子 DOPO类化合物加成到 C=C上, 生成具有式 (1 ) 结构式的化合物。
根据本领域公知常识, DOPO 化学名称为 9,10-二氢 -9-氧杂 -10-磷杂菲 - 10-氧化物。本申请所述 DOPO类化合物包含 DOPO和 DOPO衍生物。 DOPO 衍生物指 DOPO化学结构式中的苯环上, 有氢原子被其他取代基取代, 常
见的取代基有甲基、 乙基、 异丙基、 叔丁基、 氯代基等。
根据本领域公知常识, 聚酰胺也称锦纶或尼龙, 是其结构单元中含
-NH-C C -酰胺基团的高分子的总称, 通过一种或多种二元羧酸和一种或多 种二元胺, 和 /或者一种或多种氨基酸, 和 /或者一种或多种内酰胺缩合或开 环反应合成。 根据其主链的成分, 聚酰胺一般分为脂肪族聚酰胺、 芳香族 聚酰胺和半芳香族聚酰胺。 半芳香族聚酰胺是指其合成单体中至少一个单 体结构中含有芳香基团。
优选地, 所述半芳香族聚酰胺可由任意一种或几种芳香族二元羧酸与任 意一种或几种脂肪族二元胺制得, 也可由任意一种或几种芳香族二元胺与 任意一种或几种脂肪族二元羧酸制得。 体系中还可以添加任选自二元羧酸、 二元胺、 内酰胺和氨基酸中的一种或任意几种, 来制备相应性能的聚酰胺 共聚物。 添加的二元羧酸为芳香族二元羧酸和 /或脂肪族二元羧酸; 添加的 二元胺为芳香族二元胺和 /或脂肪族二元胺; 添加的内酰胺可以是脂肪族或 者芳香族内酰胺。 添加的氨基酸可以是芳香族或脂肪族氨基酸。
优选地, 所述半芳香族聚酰胺由任选自对苯二甲酸、 间苯二甲酸和萘二 甲酸中的一种或多种芳香族二元羧酸, 与任选自丁二胺、 己二胺、辛二胺、 癸二胺和 2-甲基戊二胺中的一种或多种脂肪族二元胺制得。
优选地, 所述半芳香族聚酰胺由脂肪族二元胺、 芳香族二元羧酸和脂肪 族二元羧酸制得。
优选地, 所述半芳香族聚酰胺由脂肪族二元胺与芳香族二元羧酸制得; 可选择地, 其中还可以添加脂肪族二元羧酸, 脂肪族二元羧酸的摩尔分数 占二元羧酸总量的 0~45%, 即脂肪族二元羧酸的摩尔数 / (脂肪族二元羧酸
的摩尔数 +芳香族二元羧酸的摩尔数) =0~45%。
优选地, 所述芳香族二元羧酸任选自对苯二甲酸、 间苯二甲酸和萘二甲 酸中的一种或多种; 所述脂肪族二元胺任选自丁二胺、 己二胺、 辛二胺、 癸二胺和 2-甲基戊二胺中的一种或多种; 所述脂肪族二元羧酸任选自己二 酸、 丁二酸、 癸二酸、 辛二酸中的一种或多种。
优选地, 所述聚酰胺任选自聚对苯二甲酰己二胺(简写为 PA6T)、 聚间 苯二甲酰己二胺 (简写为 PA6I)、 对苯二甲酸 /己二胺 /己内酰胺共聚物 (简 写为 PA6T/6 )、 对苯二甲酸 /己二胺 /己二酸的共聚物(简写为 PA6T/66 )、 对 苯二甲酸 /己二胺 /己二酸 /间苯二甲酸的共聚物 (简写为 PA6T/6I/66)、 聚对 苯二甲酰壬二胺 (简写为 PA9T)、 聚对苯二甲酰癸二胺 (简写为 PA10T), 聚对苯二甲酰十二二胺 (简写为 PA12T:)、 对苯二甲酸 /己二胺 /十二内酰胺共 聚物 (简写为 PA6T/12 )、 聚己二酰间苯二甲胺 (简写为 MXD6)、 对苯二 甲酸 /己二胺 /2-甲基戊二胺共聚物 (简写为 PA6T/2-MPMDT)、 对苯二甲酸 /2,2,4三甲基己二胺 /2,4,4-三甲基己二胺共聚物中的一种或几种。
半芳香族高温尼龙做成阻燃材料时,也常常添加各种助剂,包括稳定剂、 加工助剂、 抗滴落剂、 颜料、 染料、 成炭催化剂、 分散剂、 成核剂等, 同 时也可添加增强纤维或无机填料, 譬如云母石、 碳酸钙、 氧化钙、 硅石或 它们的混合物。 在一些阻燃高温尼龙制备中, 半芳香族聚酰胺中也可以添 加脂肪族聚酰胺来提高加工流动性能, 脂肪族聚酰胺是其结构单元中只含 脂肪链的一类线性聚酰胺。 当半芳香族聚酰胺中添加脂肪族聚酰胺时, 脂 肪族聚酰胺占总聚酰胺重量的百分比为 0~45%。
优选地, 所述无卤阻燃高温尼龙中含有玻璃纤维。
优选地, 所述化合物 A占无卤阻燃高温尼龙总重量的 1~40%。
优选地, 所述化合物 A占无卤阻燃高温尼龙总重量的 3~30%。
优选地, 所述化合物 A占无卤阻燃高温尼龙总重量的 5~25%。 本申请还提供了所述无卤阻燃高温尼龙的制备方法, 其特征在于, 将聚 酰胺和化合物 A, 于 250~380°C下混合后, 经冷却、 干燥, 即得所述无卤阻 燃高温尼龙。 本申请还提供了一种表面贴装元件, 其特征在于, 含有所述无卤阻燃高 温尼龙。 由于所述无卤阻燃高温尼龙具有良好的热稳定性、 化学稳定性和 机械性能, 以其为主要原料制作的表面贴装元件 (SMD) 满足表面贴装过 程 (SMT) 中高温红外回流炉悍接工艺的使用要求。 本申请所述技术方案的有益效果为:
本申请披露的无卤阻燃高温尼龙, 添加一种 DOPO衍生物作为阻燃剂。 该阻燃剂不仅阻燃效果好, 且具有良好的热稳定性和化学稳定性, 能够在 不降低高温尼龙加工流动性的同时, 克服已有0100?0阻燃剂的耐化学性 不足或者塑化性强的缺点。所制备的无卤阻燃高温尼龙, 燃烧测试 0.8毫米 达到 UL94 V-0级别, 具有良好的热稳定性、 化学稳定性和机械性能, 以其 为主要原料制作的表面贴装元件(SMD), 满足表面贴装过程(SMT) 中高 温红外回流炉悍接工艺的使用要求。
应理解, 在本申请披露的技术方案范围内, 本申请的上述各技术特征和 在下文 (如实施例)中具体描述的各技术特征之间都可以互相组合,从而构成 新的或优选的技术方案。 限于篇幅, 在此不再一一累述。
除非另行定义, 文中所使用的所有专业与科学用语与本领域熟练人员所 熟悉的意义相同。 此外, 任何与所记载内容相似或均等的方法及材料皆可 应用于本申请方法中。 文中所述的较佳实施方法与材料仅作示范之用。 具体实施方式
本申请提到的上述特征, 或实施例提到的特征可以任意组合。 本案说明 书所揭示的所有特征可与任何组合物形式并用, 说明书中所揭示的各个特 征, 可以被任何提供相同、 均等或相似目的的替代性特征取代。 因此除有 特别说明, 所揭示的特征仅为均等或相似特征的一般性例子。
下面结合实施例, 进一步阐述本发明。 应理解, 这些实施例仅用于说明 本发明而不用于限制本发明的范围。 下列实施例中未注明具体条件的实验 方法, 通常按照常规条件或按照制造厂商所建议的条件。
未做特殊说明的情况下, 本申请使用 Bruker 400MHz AVANCE III型磁 共振仪器上对实施例中所得产品进行 ^-NMR和 31P-NMR表征。 磷谱表征 条件为氢去耦, 预延期 Dl = 10秒, 扫描次数大于 16次, 溶剂 CDC13, 使 用 85%磷酸做定位标样。
实施例中,化合物 A产率的计算方法为:(产物重量 /产物理论重量)χ 100%。 其中产物理论重量是基于原料中芳基酮的量计算得到。
未做特殊说明的情况下, 本申请所使用原料, 均通过商业途径购买, 不
经特殊处理直接使用。
实施中所用原料如下
PA66 (又称聚酰胺 66或尼龙 66 ): 美国杜邦 70G30L NC010
PPA (高温尼龙, 对苯二甲酸和间苯二甲酸以及脂肪族二元羧酸同脂肪族 二胺的共聚物, 其中芳香族二元羧酸占总二元羧酸的摩尔分数大于等于 55%。): 美国杜邦 HTN 51G35HSL NC010
MPP (三聚氰胺焦磷酸盐): 苏州凯马化学科技有限公司
抗滴落剂 (PTFE, 聚四氟乙烯): 上海尚聚化工科技有限公司 SN3306 云母: 安徽云母粉厂, 400目
硅灰石: 江西科特精细粉体有限公司, 800目
燃烧测试标准: GB/T 2408-2008标准
抗氧剂 1010: 又称四 [β (3, 5-二叔丁基 -4-羟基苯基)丙酸]季戊四醇酯, CAS号为 6683-19-8, 分子式为〇73 。8012。 实施例 1具有式(2) 结构化合物 Α的制备
DOPO ( 86.40 g, 0.40 mol ) , 苯乙酮 (24.05 g, 0.20 mol )和 10毫升二 甲苯加入到装有温度计, 分水器, 磁搅拌子和恒压漏斗的三口烧瓶中。 在 氮气保护下, 混合液加热到 154°C, 开始滴加三氯氧磷。 P0C13 (30.25 g) 在 25小时内慢慢滴加到反应液中, 在分水器中收集馏分, 保持反应温度在 154-160° (:。 滴完三氯氧磷后, 保温半小时。 冷却, 加入 120 g异丙醇, 回 流下搅拌, 粗产物软化后大部分溶解, 体系浑浊。 停止搅拌、 冷却, 静置 一段时间后产物大量析出。 抽滤, 固体产物先用少量异丙醇洗涤, 收集滤
液, 再用适量去离子水洗涤三次, 产物为白色固体粉末, 收集后 iio°c下干 燥 13 h, 得到 89g产物, 产率为 83.2%。
在磁共振仪器上对所得产品进行 H 谱和 P 谱的表征, 其磷谱数据为 31PNMR( 85%H3P04 =0 pm): 34.2-37.0 pm (多峰);其氢谱数据为 ^NMR
(CDC13, TMS ) : 6.2-8.0(多峰, 21H), 3.3-3.8 (多峰, 1H), 2.5-3.0 (多峰, 2H 实施例 2具有式(3) 结构化合物的制备
将 DOPO (86.40 g, 0.40 mol) 和萘乙酮 (34.04g, 0.20 mol) 加入到装 有温度计, 磁搅拌子和恒压漏斗的三口烧瓶中。 在氮气保护下, 混合液加 热到 170°C, 开始滴加三氯氧磷。 P0C13 ( 15.96 g) 在 20小时内慢慢滴加 到反应液中, 保持反应温度在 170-180度。 滴完三氯氧磷后, 保温半小时。 31P核磁谱图显示无原料。冷却,加 50ml 90%的乙醇溶解,然后滴加约 60ml 2.5%的 Na2C03溶液将反应液 pH调至 6~7, 回流半小时后抽滤得白色固体 产物。 产率 70.6%。
在磁共振仪器上对所得产品进行 H 谱和 P 谱的表征, 其磷谱数据为 31PNMR( 85%H3P04 =0 ppm): 34.0-37.0 ppm (多峰);其氢谱数据为 ^NMR (CDC13) : 6.0-8.0(多峰, 23H), 3.6-3.8 (多峰, 1H), 2.8-3.1 (多峰, 2H)。 实施例 3
将实施例 1中所得化合物 A、 PPA、 抗氧化剂 1010按照 9:51:0.12的重 量比例, 在转速为 50转 /分钟的密炼机中混合, 设置温度为 300°C, 5分钟
后取出冷却、 干燥。 然后将其填充于模具中, 在 280°C的平板硫化机预热 10分钟, lOMPa保压 4分钟后, 冷压。 待其冷却后切样、 测试。 0.8mm样 品的阻燃级别 UL94 V-0。 实施例 4
将实施例 2中所得化合物 A、 PPA、 抗氧化剂 1010按照 12:48:0.12的重 量比例, 在转速为 50转 /分钟的密炼机中混合, 设置温度为 300°C, 5分钟 后取出冷却、 干燥。 然后将其填充于模具中, 在 280°C的平板硫化机预热 10分钟, lOMPa保压 4分钟后, 冷压。 待其冷却后切样、 测试。 0.8mm样 品的阻燃级别 UL94 V-0。 实施例 5
将实施例 1 中所得化合物 A、 PA66、 PPA、 抗氧化剂 1010 按照 12:4.77:42.93:0.12的重量比例, 在转速为 50转 /分钟的密炼机中混合, 设置 温度为 285°C, 5分钟后取出冷却、干燥。然后将其填充于模具中, 在 290°C 的平板硫化机预热 10分钟, lOMPa保压 4分钟后,冷压。待其冷却后切样、 测试。 0.8mm样品的阻燃级别 UL94 V-0。 实施例 6
将实施例 1 中所得化合物 A、 PA66、 PPA、 MPP、 抗滴落剂 PTFE、 抗 氧化剂 1010按照 9:8.7:36:6:0.3:0.12的重量比例, 在转速为 50转 /分钟的密 炼机中混合, 设置温度为 285°C, 5分钟后取出冷却、 干燥。 然后将其填充
于模具中, 在 290°C的平板硫化机预热 10分钟, lOMPa保压 4分钟后, 冷 压。 待其冷却后切样、 测试。 0.8mm样品的阻燃级别 UL94 V-0。 本发明虽然以较佳实施例公开如上, 但并不是用来限定权利要求, 任何 本领域技术人员在不脱离本发明精神和范围内, 都可以做出可能的变动和 修改, 因此本发明的保护范围应当以本发明权利要求所界定的范围为准。
Claims
1、 一种无卤阻燃高温尼龙, 其特征在于, 含有聚酰胺和化合物 A; 所述聚酰胺任选自半芳香族聚酰胺、 半芳香族聚酰胺与脂肪族聚酰胺的 混合物、 半芳香族聚酰胺与脂肪族聚酰胺的共聚物;
化合物 A具有如式 (1 ) 所示的化学结构式:
Ar任选自 C3 C18的杂芳基或 C6 C18的芳基;
和 独立地任选自氢、 C1 C18的垸基、 C3 C18的杂芳基、 C6 C18 的芳基;
R3, , R5和 Re独立地任选自氢、 C1-C18的垸基、 C3 C18的杂芳基、 C6-C18的芳基;
m, n, k和 p独立地任选自 0, 1, 2, 3, 4;
所述芳基或杂芳基芳香环上的任意氢原子可以独立被任意 C1-C18的垸 基取代。
2、 根据权利要求 1 所述的无卤阻燃高温尼龙, 其特征在于, 所述化合 物 A结构式中杂芳基任选自呋喃基、苯并呋喃基;芳基任选自苯基、萘基、 茚基、 芴基、 甲基苯基、 乙基苯基、 丙基苯基、 丁基苯基、 二甲基苯基、
异丙基苯基、 异丁基苯基或叔丁基苯基。
3、 根据权利要求 1 所述的无卤阻燃高温尼龙, 其特征在于, 所述化合 物 A的结构式任选自式(2)、 式(3)、 式(4)、 式(5)、 式(6)和式(7) 中的一种,
(2)
(3)
(4)
(5)
4、 根据权利要求 1 所述的无卤阻燃高温尼龙, 其特征在于, 所述半芳 香族聚酰胺由任意一种或几种芳香族二元羧酸与任意一种或几种脂肪族二
元胺制得, 或者由任意一种或几种芳香族二元胺与任意一种或几种脂肪族 二元羧酸制得; 优选地, 所述半芳香族聚酰胺由任选自对苯二甲酸、 间苯 二甲酸和萘二甲酸中的一种或多种芳香族二元羧酸, 与任选自丁二胺、 己 二胺、 辛二胺、 癸二胺和 2-甲基戊二胺中的一种或多种脂肪族二胺制得。
5、 根据权利要求 1 所述的无卤阻燃高温尼龙, 其特征在于, 所述半芳 香族聚酰胺由脂肪族二元胺、 芳香族二元羧酸和脂肪族二元羧酸制得。
6、 根据权利要求 5所述的无卤阻燃高温尼龙, 其特征在于, 所述芳香 族二元羧酸任选自对苯二甲酸、 间苯二甲酸和萘二甲酸中的一种或多种; 所述脂肪族二元胺任选自丁二胺、 己二胺、 辛二胺、 癸二胺和 2-甲基戊二 胺中的一种或多种; 所述脂肪族二元羧酸任选自己二酸、丁二酸、癸二酸、 辛二酸中的一种或多种。
7、 根据权利要求 1 所述的无卤阻燃高温尼龙, 其特征在于, 所述半芳 香族聚酰胺任选自聚对苯二甲酰己二胺、 聚间苯二甲酰己二胺、 对苯二甲 酸 /己二胺 /己内酰胺共聚物、 对苯二甲酸 /己二胺 /己二酸的共聚物、 对苯二 甲酸 /己二胺 /己二酸 /间苯二甲酸的共聚物、聚对苯二甲酰壬二胺、聚对苯二 甲酰癸二胺, 聚对苯二甲酰十二二胺、 对苯二甲酸 /己二胺 /十二内酰胺共聚 物、 聚己二酰间苯二甲胺、 对苯二甲酸 /己二胺 /2-甲基戊二胺共聚物、 对苯 二甲酸 /2,2,4三甲基己二胺 /2,4,4-三甲基己二胺共聚物中的一种或几种。
8、权利要求 1所述的无卤阻燃高温尼龙,其特征在于,含有玻璃纤维; 所述化合物 A占无卤阻燃高温尼龙总重量的 1~40%,优选的范围为 3~30%, 进一步优选的范围为 5~25%。
9、 制备权利要求 1-8所述任一无卤阻燃高温尼龙的方法, 其特征在于,
将聚酰胺和化合物 A, 于 250~380°C下混合, 经冷却、 干燥后, 即得所述无 卤阻燃高温尼龙。
10、 一种表面贴装元件, 其特征在于, 含有权利要求 1-8所述任一无卤 阻燃高温尼龙。
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