CN101575408B - Polytriazinyl compounds as flame retardants and light stabilizers - Google Patents

Polytriazinyl compounds as flame retardants and light stabilizers Download PDF

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CN101575408B
CN101575408B CN 200910140579 CN200910140579A CN101575408B CN 101575408 B CN101575408 B CN 101575408B CN 200910140579 CN200910140579 CN 200910140579 CN 200910140579 A CN200910140579 A CN 200910140579A CN 101575408 B CN101575408 B CN 101575408B
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B·L·卡尔
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Mca技术有限公司
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Abstract

得自1,3,5-三嗪的无卤素自熄性低聚物或聚合物,其具有以下通式I,其中或环中包含至少一个氮原子的杂环基团,该基团通过一个所述氮原子连接至三嗪环,R2是烷基或环烷基,R1是以下通式的哌嗪二价基或以下类型的二价基或,R2是烷基或环烷基,n是2至30的整数,包括端值,m是2至6的整数,包括端值,p是2至12的整数,包括端值,和X1=OH、NH2或X,其中X和X1可以相同或不同,X2=氢或C1-C4烷基,并涉及一种生产通式I化合物的无溶剂方法,以及该自熄性低聚或聚合物作为阻燃剂和光稳定剂用于热塑性聚合物例如聚丙烯或再生纤维素或聚酯的用途。 From self-extinguishing halogen-free oligomeric or polymeric 1,3,5-triazine having the general formula I, wherein rings or heterocyclic group containing at least one nitrogen atom, the group by a the nitrogen atom to the triazine ring a, R2 is alkyl or cycloalkyl, R1 is a divalent piperazinyl group, or the following divalent groups of the general formula or, R2 is an alkyl or cycloalkyl alkyl, n is integer from 2 to 30, inclusive, m is an integer from 2 to 6, inclusive, p is an integer from 2 to 12, inclusive, and X1 = OH, NH2, or X, wherein X and X1 may be the same or different, X2 = hydrogen or C1-C4 alkyl group, and to a method for producing a compound of formula I in a solvent-free, self-extinguishing and flame retardant and as oligomeric or polymeric light stabilizers for thermoplastic polymers such as poly the use of propylene or regenerated cellulose or polyester.

Description

用作阻燃剂和光稳定剂的聚三嗪基化合物 Used as flame retardants and light stabilizers polytriazine compound

技术领域 FIELD

[0001] 本发明涉及通式I的无卤素化合物, [0001] The present invention relates to a halogen-free compound of formula I,

[0002] [0002]

Figure CN101575408BD00041

[0003] 其中 [0003] in which

[0004] [0004]

/ /

Figure CN101575408BD00042

[0005] 或环中包含至少一个氮原子的杂环基团,该基团通过一个所述氮原子连接至三嗪环,R2是烷基或环烷基,R:是以下通式的哌嗪的二价基 [0005] or a heterocyclic ring group containing at least one nitrogen atom, the group is attached to the triazine ring through a nitrogen atom of the, R2 is alkyl or cycloalkyl, R: is a piperazine of the general formula divalent

[0006] [0006]

Figure CN101575408BD00043

[0007] 或以下类型的二价基 [0007] or a divalent group of the following types

[0008] [0008]

Figure CN101575408BD00044

[0009] η是2至30的整数,包括端值,m是2至6的整数,包括端值,ρ是2至12的整数,包括端值,x2是氢或C1-C;烷基,和 [0009] η is an integer of 2 to 30, inclusive, m is an integer from 2 to 6, inclusive, [rho] is an integer from 2 to 12, inclusive, x2 is hydrogen or C1-C; alkyl, with

[0010] \ = 0Η、ΝΗ2*Χ,其中XJPX可以相同或不同。 [0010] \ = 0Η, ΝΗ2 * Χ, which may be the same or different XJPX.

[0011] 本发明还涉及生产通式I化合物的方法,优选不使用任何有机溶剂,优选在表面活性剂的存在下。 [0011] The present invention further relates to a method of producing a compound of formula I, preferably without using any organic solvent, preferably in the presence of the surfactant.

发明内容 SUMMARY

[0012] 本发明方法的第一步骤是根据现有技术,在-10°c至+10°C温度范围,在pH值为5至7下,在极性溶剂例如丙酮、水等中,但是优选不使用任何有机溶剂,使氰尿酰卤与通式R2-NH2的胺或与环中包含氮原子的杂环化合物以摩尔比为1: 1进行反应,以获得2,6- 二氯-1,3,5-三嗪的4-氨基衍生物。 [0012] a first step of the method of the present invention is according to the prior art, to a temperature range of + 10 ° C, at a pH at -10 ° c under 5 to 7, in a polar solvent such as acetone, water and the like for example, but preferred not to use any organic solvent, cyanuric halide and an amine of formula R2-NH2 or a heterocyclic ring compound containing a nitrogen atom in a molar ratio of 1: 1 were reacted to obtain 2,6-dichloro - 4-amino-1,3,5-triazine derivative.

[0013] 不用分离,然后在热条件下,始终在水或极性溶剂中,但是优选不使用任何有机溶齐U,使中间悬浮液与通式H2N-(CH2)m-NH2的胺、与哌嗪或其烷基取代衍生物、与4-氨基-2,2,6,6_四甲基哌啶或N,-双-(2,2,6,6-四甲基-4-哌啶基)-l,6-己二胺、或与这些化合物的混合物反应,其中三嗪衍生物与胺和/或哌嗪之间的摩尔比等于1: 1。 [0013] without isolation and under hot conditions, always in the water or a polar solvent, but preferably without using any organic solvent together U, the suspension of the intermediate of the general formula H2N- (CH2) m-NH2 amine, and alkyl group or a substituted piperazine derivative, with 4-amino -2,2,6,6_ tetramethyl piperidine or N, - bis - (2,2,6,6-tetramethyl -4- piperidinyl) -l, 6- hexanediamine, or with mixtures of these compounds, wherein the molar ratio between triazine derivative and amine and / or piperazine equal to 1: 1.

[0014] 然后通过在碱例如过量HXi和/或碱金属氢氧化物的存在下,在90°C至150°C的温度下,更优选100°C至130°c的温度下,使中间化合物与通式HXi的化合物反应,得到通式I的化合物。 [0014] then in the presence of excess base such HXi and / or alkali metal hydroxide, at a temperature to 90 ° C and 150 ° C, more preferably at a temperature of 130 ° c C to 100 °, the intermediate compound with a compound of formula HXi, to give a compound of general formula I.

[0015] 因此,本发明的另一个目的是通过在两个或三个步骤中氰尿酰卤与适当胺和/或杂环化合物的缩合,生产具有以下通式的不溶于水的1,3,5-三嗪衍生物低聚物或聚合物的方法: [0015] Accordingly, a further object of the present invention is achieved by two or three steps cyanuric halide the condensation with the appropriate amine and / or heterocyclic compound, having the general formula producing a water-insoluble 1,3 , 5-triazine derivative of a polymer or oligomer method:

[0016] [0016]

Figure CN101575408BD00051

[0017] 其中 [0017] in which

[0018] [0018]

Figure CN101575408BD00052

[0019] 或环中包含至少一个氮原子的杂环基团,该基团通过一个所述氮原子连接至三嗪环,R2是烷基或环烷基,R:是以下通式的哌嗪的二价基 [0019] or a heterocyclic ring group containing at least one nitrogen atom, the group is attached to the triazine ring through a nitrogen atom of the, R2 is alkyl or cycloalkyl, R: is a piperazine of the general formula divalent

[0020] [0020]

Figure CN101575408BD00053

(Y) (Y)

[0024] η是2至30的整数,包括端值,m是2至6的整数,包括端值,ρ是2至12的整数,包括端值,x2是氢或C1-C;烷基,和 [0024] η is an integer of 2 to 30, inclusive, m is an integer from 2 to 6, inclusive, [rho] is an integer from 2 to 12, inclusive, x2 is hydrogen or C1-C; alkyl, with

[0025] \ = 0Η、ΝΗ2或父,其中\和X可以相同或不同。 [0025] \ = 0Η, ΝΗ2 or parent, where \ and X may be the same or different.

[0026] 为了保持反应混合物为平稳的悬浮液,优选加入表面活性剂例如十二烷基苯磺酸。 [0026] In order to maintain the reaction mixture as a stable suspension, is preferably added surfactants such as dodecylbenzene sulfonic acid. 得到的通式I化合物是具有很高熔点和最小卤素含量的白色粉末。 Compound of formula I is obtained having minimum halogen content and a very high melting point white powder. 可以将其研磨为小颗粒,然后准备与其它阻燃化合物如磷酸铵或磷酸胺一起并入热塑性聚合物。 Which can be milled into small particles, and then prepared with other flame retardant compounds such as ammonium phosphate or amine phosphate incorporated with a thermoplastic polymer. [0027] 可以根据已知的方法生产本发明自熄性组合物:例如,首先密切地将磷酸铵或磷酸胺与细磨的三嗪含氮化合物(优选具有低于75微米的颗粒)混合,并将如此得到的混合物在涡轮式混合器中加入热塑性聚合物中,以形成均匀混合物,然后将该混合物挤出并造粒。 [0027] according to methods known in the production of self-extinguishing composition of the present invention: e.g., a first closely ammonium or amine phosphate with the finely ground triazine nitrogenous compound (preferably having particles below 75 microns) were mixed, and the mixture thus obtained was added in a turbo mixer thermoplastic polymer to form a homogeneous mixture, and the mixture was then extruded and pelletized. 根据任何已知的模制技术,可以将如此得到的颗粒产品转变成多种制品。 According to any known molding technique, granular product thus obtained can be converted into a variety of articles. 本发明阻燃添加剂还适用于阻燃涂料领域。 Flame retardant additives of the present invention is also applicable to a fire-retardant coatings.

[0028] 为测定包含阻燃添加剂的聚合组合物自熄性能,可以进行如下操作:在M00RE平板压力机中,通过以40kg/cm2压力,在合适的温度下操作7分钟,将颗粒产品模制成3毫米(1/8英寸)厚的板。 [0028] To determine the self-extinguishing properties of the polymeric composition containing the flame retardant additive, may be as follows: In M00RE plate press, by 40kg / cm2 pressure, at a suitable operating temperature for 7 minutes, and the pellets molded product into 3 mm (1/8 inch) thick plate. 然后根据UL-94方法测试该板。 The plate was then tested according to UL-94 method.

[0029] 其中& = Y的通式(I)聚三嗪化合物是有用和有价值的试剂,可用于改善合成聚合物对光、热和氧化的稳定性,所述合成聚合物例如为高和低密度聚乙烯、聚丙烯、乙烯-丙烯共聚物、乙烯-醋酸乙烯酯共聚物、聚丁二烯、聚异戊二烯、聚苯乙烯、苯乙烯-丁二烯共聚物、丙烯腈-丁二烯-苯乙烯共聚物、氯乙烯和偏二氯乙烯聚合物和共聚物、聚甲醛、聚对苯二酸乙二醇酯、尼龙66、尼龙6、尼龙12、聚氨酯、不饱和聚酯。 [0029] wherein Y & = formula (I) of polytriazine compounds are useful and valuable agents, synthetic polymers can be used to improve the optical, thermal and oxidative stability of the synthetic polymers such as high and low density polyethylene, polypropylene, ethylene - propylene copolymer, ethylene - vinyl acetate copolymer, polybutadiene, polyisoprene, polystyrene, styrene - butadiene copolymer, acrylonitrile - D diene - styrene copolymers, vinyl chloride and vinylidene chloride polymers and copolymers, polyoxymethylene, polyethylene terephthalate, nylon 66, nylon 6, nylon 12, polyurethane, unsaturated polyester.

[0030] 其中& = Y的通式(I)化合物特别可用作聚烯烃和更特别用作具有减少厚度的聚烯烃制品,例如纤维和薄膜的光稳定剂。 [0030] where & = Y in formula (I) compounds, in particular polyolefins, and more particularly useful as a polyolefin article having a reduced thickness, light stabilizers e.g. fibers and films. 令人惊讶的是,当与水或表面活性剂水溶液接触时,很难从所述薄制品提取出所述化合物。 Surprisingly, when contacted with water or an aqueous surfactant solution, it is difficult to extract the compound from the thin article.

[0031] 其中札=Y的通式⑴化合物可以采用按照多种比例与合成聚合物的混合物使用,其取决于聚合物性质、最终用途和存在的其它添加剂。 [0031] wherein Formula sheaf of ⑴ = Y compound can be employed using a mixture of synthetic polymers in various proportions, depending on the nature of the polymer, the end use and the presence of other additives.

[0032] 相对于聚合物重量,通常优选使用0.01至5重量%其中& = Y的通式(I)化合物,更优选0.1至1%。 [0032] with respect to the weight of the polymer, generally preferably 0.01 to 5% by weight compound of formula wherein Y, & (I) =, more preferably 0.1 to 1%.

[0033] 可以用多种方法例如以粉末形式干混合,或以溶液或淤浆形式湿法,将其中札=Y的通式(I)化合物加入聚合材料组合物中。 [0033] Various methods can be used, for example, dry mixing in powder form, or as a solution or a wet slurry, wherein the compound of formula sheaf = Y (I) is added to the polymeric material in the composition. 在所述操作中,合成聚合物可以采用粉末、颗粒、溶液、淤浆或乳液的形式。 In such operations, the polymer can be synthesized in the form of powders, granules, solutions, emulsions or slurry employed.

[0034] 用其中& = Y的通式(I)的产品稳定的聚合物可以用于生产模制品、薄膜、带材、纤维、单丝等。 [0034] where a = & stabilized polymer product Y is formula (I) may be used for the production of molded articles, films, tapes, fibers, monofilaments and the like.

[0035] 其中& = Y的通式(I)化合物与合成聚合物的混合物可以任选加入其它添加剂,例如抗氧化剂、紫外线吸收剂、镍稳定剂、颜料、电荷剂(charges)、塑化剂、抗静电剂、阻燃剂、润滑剂、防锈剂、金属抑制剂等。 [0035] wherein Y & = formula (I), a mixture of synthetic polymer compound may be optionally added other additives, such as antioxidants, ultraviolet absorbers, nickel stabilizers, pigments, charge agents (charges), plasticizer , antistatic agents, flame retardants, lubricants, rust inhibitors, metal inhibitors.

[0036] 通式I中,R2优选是包含1至20个碳原子的烷基或包含6至20个碳原子的环烷基,R:优选是哌嗪的二价基或二胺的二价基,其中m是2至6的整数,包括端值,η优选是8至20的整数,ρ优选是4至10的整数,包括端值。 [0036] In Formula I, R2 is preferably an alkyl group containing 1 to 20 carbon atoms or a cycloalkyl group having 6 to 20 carbon atoms, R: is preferably a divalent group of piperazine or a divalent diamine group, wherein m is an integer from 2 to 6, inclusive, [eta] is preferably an integer of 8 to 20, [rho] is preferably an integer from 4 to 10, inclusive.

[0037] 烷基的实例是甲基、乙基、丙基、正丁基、异丁基、己基、辛基、癸基、十二烷基、环己基、丙基-环己基、丁基-环己基、癸基环己基。 [0037] Examples of alkyl groups are methyl, ethyl, propyl, n-butyl, isobutyl, hexyl, octyl, decyl, dodecyl, cyclohexyl, propyl - cyclohexyl, butyl - cyclohexyl, decyl cyclohexyl. 定义为X的杂环基团的实例是吗啉、哌啶和哌嗪。 Examples of X is defined as the heterocyclic group are morpholine, piperidine, and piperazine. 对于&的二胺的实例为乙二胺、四亚甲基二胺、五亚甲基二胺、六亚甲基二胺。 Examples for & diamine is ethylene diamine, tetramethylene diamine, pentamethylene diamine, hexamethylene diamine.

[0038] 优选的通式I化合物为& =六亚甲基二胺、哌嗪和烷基取代哌嗪的那些化合物,以及其中\和X为相同并具有吗啉基、哌啶基或哌嗪基的通式I化合物。 [0038] Preferred compounds of formula I is & = hexamethylenediamine, piperazine and alkyl-substituted piperazines are those compounds, and wherein \ and X are the same and having a morpholinyl, piperidinyl or piperazinyl group of formula I compounds.

[0039] 下列实施例说明根据通式A和I某些化合物的制备。 [0039] The following examples illustrate the preparation of certain compounds according to formula A and I. 除非另作说明,该制备中指出的全部份数都是指重量份。 Unless otherwise noted, all parts are indicated in this preparation means parts by weight.

[0040] 实施例1[0041] 向反应器装入150份水、150份冰和0.2份十二烷基苯磺酸。 [0040] Example 1 [0041] 150 parts of water was charged to the reactor, 150 parts of ice and 0.2 parts of dodecylbenzenesulfonic acid. 然后在搅拌条件下,在15分钟内加入74份氰尿酰氯。 Then with stirring, 74 parts of cyanuric chloride was added over 15 minutes. 搅拌混合物15分钟,得到均匀的悬浮液。 The mixture was stirred for 15 minutes to obtain a uniform suspension. 形成悬浮液后,同时加入溶解在150份水中的34.9份吗啉和21.2份碳酸钠(100%基础(100% basis)),同时保持pH值为5至7,温度最大值为0-5°C。 After forming the suspension, while adding 150 parts of water dissolved in 34.9 parts of morpholine and 21.2 parts of sodium carbonate (100% of the basal (100% Basis)), while maintaining a pH of 5-7, the maximum temperature of 0-5 ° C. 加入时间为30分钟。 Addition time was 30 minutes. 完成加入后,在0-5°C搅拌反应混合物30分钟。 After complete addition, the reaction mixture was stirred for 30 minutes at 0-5 ° C.

[0042] [0042]

Figure CN101575408BD00071

[0043] 向得到的II的白色悬浮液中加入34.9份哌嗪,将混合物加热至40°C并在40°C搅拌30分钟。 [0043] 34.9 parts of piperazine were added to the resulting white suspension II, the mixture was heated to 40 ° C and stirred at 40 ° C 30 min. 其后,在15分钟内缓慢加入溶解在100份水中的16份氢氧化钠(100%基础),从而保持温度在40°C。 Thereafter, it was added slowly over 15 minutes in 100 parts of water were dissolved 16 parts of sodium hydroxide (100% basis), thereby maintaining the temperature at 40 ° C. 在40°C搅拌15分钟后,加热混合物至95°C。 After stirring for 15 minutes 40 ° C, the mixture was heated to 95 ° C. 温度达到95°C后,在两个小时内加入溶解在100份水中的第二部分16份氢氧化钠(100%基础)。 After the temperature reached 95 ° C, was added within two hours were dissolved in 100 parts of water, 16 parts of a second portion of sodium hydroxide (100% basis). 在压力下在130°C下加热得到的悬浮液24小时及最终pH应该为碱性。 The suspension was 24 hours and the final pH at a pressure heating at 130 ° C to give be alkaline. 在90°C过滤悬浮液,并用热水充分洗涤该产品直到pH为中性。 The suspension was filtered at 90 ° C, and the product is washed thoroughly with hot water until the pH was neutral. 在100°C干燥该产品24小时,直到重量恒定。 The product was dried for 24 hours at 100 ° C, until constant weight. 得到109份下式的化合物: To give 109 parts of a compound of the formula:

[0044] [0044]

Figure CN101575408BD00072

[0045] 其中η = 10,具有下列特征: [0045] where η = 10, having the following characteristics:

[0046] 外观:白色粉末 [0046] Appearance: White powder

[0047] 熔点:高于290°C [0047] Melting point: above 290 ° C

[0048] 有机氯含量(元素分析和水解方法):1.42%。 [0048] an organic chlorine content (elemental analysis and hydrolysis method): 1.42%.

[0049] 实施例2 [0049] Example 2

[0050] 在具有冷凝器、搅拌器和温度计的反应器中,室温下放置400份吗啉。 [0050] In a reactor having a condenser, a stirrer and a thermometer, 400 parts of morpholine are placed at room temperature. 加入200份式III的化合物(包含1.5%氯),并加热所述混合物至120°C。 Was added 200 parts of the compound of formula III (containing 1.5% chlorine), and the mixture was heated to 120 ° C. 搅拌所述混合物12小时。 The mixture was stirred for 12 hours. 降温至室温后,将混合物倾倒在1000份冰和包含3.5份100%氢氧化钠的1000份水上。 After cooling down to room temperature, the mixture was poured into 1000 parts of ice and 1000 parts of water containing 3.5 parts of 100% sodium hydroxide. 过滤得到的悬浮液;在室温下用水充分洗涤,直到pH为中性。 The resulting suspension was filtered; washed well with water at room temperature until the pH was neutral. 在100°C干燥24小时,直到重量恒定。 Dried for 24 hours at 100 ° C, until constant weight. 得到230份下式Ilia的化合物: To give 230 parts of the compound of formula Ilia:

[0051] [0051]

Figure CN101575408BD00081

[0052] 其中η = 10,具有下列特征: [0052] where η = 10, having the following characteristics:

[0053] Cl 含量(AOX):< 0.01% [0053] Cl content (AOX): <0.01%

[0054] 颜色:白色 [0054] Color: White

[0055]熔点:高于 290°C。 [0055] Melting point: above 290 ° C.

[0056] 实施例3 [0056] Example 3

[0057] 在具有冷凝器、搅拌器和温度计的反应器中,室温下放置400份哌嗪。 [0057] In a reactor having a condenser, a stirrer and a thermometer, 400 parts of piperazine are placed at room temperature. 加入200份根据美国专利4504610实施例3制备的式III的化合物(包含1.72%氯),并加热混合物至100°C。 200 parts of the compound of formula III prepared according to Example 3 of U.S. Patent No. 4,504,610 of embodiment (containing 1.72% chlorine), and the mixture was heated to 100 ° C. 搅拌所述混合物12小时。 The mixture was stirred for 12 hours. 降温至室温后,将混合物倾倒在1000份冰和包含3.2份100%氢氧化钠的1000份水上。 After cooling down to room temperature, the mixture was poured into 1000 parts of ice and 1000 parts of water containing 3.2 parts of 100% sodium hydroxide. 过滤得到的悬浮液;在室温下用水充分洗涤,直到pH为中性。 The resulting suspension was filtered; washed well with water at room temperature until the pH was neutral. 在100°C干燥24小时,直到重量恒定。 Dried for 24 hours at 100 ° C, until constant weight. 得到203份下式Illb的化合物: To give 203 parts of the compound of the formula Illb:

[0058] [0058]

Figure CN101575408BD00082

[0059] 其中η = 10,具有下列特征: [0059] where η = 10, having the following characteristics:

[0060] Cl 含量(aox):< 0.01% [0060] Cl content (aox): <0.01%

[0061] 颜色:=灰白色 [0061] Color: gray =

[0062]熔点:高于 290°C。 [0062] Melting point: above 290 ° C.

[0063] 实施例4 [0063] Example 4

[0064] 在具有冷凝器、搅拌器和温度计的反应器中,于室温下放置4份氢氧化钠(100%基础)、0.5份十二烷基苯磺酸和1000份水。 [0064] In a reactor having a condenser, a stirrer and a thermometer, placed 4 parts of sodium hydroxide (100% basis) at room temperature, 0.5 parts of dodecylbenzenesulfonic acid and 1000 parts of water. 加入200份式III的化合物(包含1.5%氯),并加热所述混合物至98°C。 Was added 200 parts of the compound of formula III (containing 1.5% chlorine), and the mixture was heated to 98 ° C. 在130°C加热得到的悬浮液12小时,最终pH应该为碱性。 At 130 ° C the resulting suspension was heated for 12 hours final pH should be basic. 在95°C过滤所述悬浮液,并用热水充分洗涤,直到pH为中性。 At 95 ° C the filtered suspension, and thoroughly washed with hot water until the pH was neutral. 在100°C干燥产物24小时,直到重量恒定。 The product was dried at 100 ° C for 24 hours until constant weight. 得到237份下式IIIc的化合物 To give 237 parts of a compound of formula IIIc

[0065] [0065]

Figure CN101575408BD00091

[0066] 其中n = 10,具有下列特征: [0066] wherein n = 10, having the following characteristics:

[0067] Cl 含量:<0.01% [0067] Cl content: <0.01%

[0068] 颜色:白色 [0068] Color: White

[0069]熔点:高于 290°C。 [0069] Melting point: above 290 ° C.

[0070] 实施例5 [0070] Example 5

[0071 ] 使用12份氢氧化铵(大约30 % )代替实施例4中的4份氢氧化钠(100 %基础),并在封闭反应器中进行反应,得到通式Illd的化合物 [0071] Using 12 parts of ammonium hydroxide (approximately 30%) in place of Example 44 parts of sodium hydroxide (100% basis) embodiment, and reaction was carried out in a closed reactor, to give a compound of formula Illd

[0072] [0072]

Figure CN101575408BD00092

[0073] 其中η = 10,具有下列特征: [0073] where η = 10, having the following characteristics:

[0074] Cl 含量:<0.01% [0074] Cl content: <0.01%

[0075] 颜色:灰白色 [0075] Color: white

[0076]熔点:高于 290°C。 [0076] Melting point: above 290 ° C.

[0077] 实施例6 [0077] Example 6

[0078] 将400份2V的水、400份碎冰和0.5份十二烷基苯磺酸装入具有搅拌器、温度计、滴液漏斗和冷却浴的2-升烧瓶,随后在30分钟内加入110.6份氰尿酰氯。 [0078] 2V to 400 parts water, 400 parts of crushed ice and 0.5 parts of dodecylbenzenesulfonic acid were charged into a stirrer, a thermometer, a 2 liter dropping funnel and a cooling bath, and then added over 30 minutes 110.6 parts of cyanuric chloride. 搅拌混合物15分钟,直至得到均匀的悬浮液。 The mixture was stirred for 15 minutes until a homogeneous suspension. 同时外部冷却,并保持pH值为5至7之间,温度为_2°C至+2°C,同时进料200份水中的51.6份哌啶和200份水中的31.8份碳酸钠(100%基础)。 Meanwhile external cooling, and a pH between 5 to 7 maintained at a temperature of _2 ° C to + 2 ° C, while feeding 200 parts of water, 51.6 parts of piperidine in 200 parts of water and 31.8 parts of sodium carbonate (100% basis). 在2°C搅拌所述混合物15分钟。 At 2 ° C and the mixture was stirred for 15 minutes. 过滤如此得到的白色产物,然后用水洗涤。 Thus obtained white product was filtered and washed with water. 得到525份滤饼,其固体含量为25.5%,相当于134份干燥材料,相应于理论收率96%。 To obtain 525 parts of cake solids content of 25.5%, corresponding to 134 parts of dry material, corresponding to 96% of the theoretical yield.

[0079] 在50°C真空下干燥10份样品后,得到2.55份2.6-二氯-4-哌啶-1,3,5-三嗪(IV)(熔点88-88.5°C )。 [0079] at 50 ° C for 10 samples dried in vacuo to give 2.55 parts of 2,6-dichloro-4-piperidine-1,3,5-triazine (IV) (m.p. 88-88.5 ° C).

[0080] [0080]

Figure CN101575408BD00101

[0081 ] 通过元素分析和NMR证实该化合物的结构。 The structure of the compound [0081] was confirmed by elemental analysis and NMR.

[0082] 将400份水和0.1份十二烷基苯磺酸加入装有搅拌器、温度计和加热浴的1升反应器。 [0082] 400 parts of water and 0.1 parts of dodecylbenzenesulfonic acid was added with stirrer, thermometer, and heating bath 1 liter reactor. 然后在20°C向其中加入46.6份产物IV和17.2份哌嗪,并由于放热反应使温度升高至30°C。 Then 20 ° C and thereto were added 46.6 parts of the product and 17.2 parts of piperazine IV, and due to the exothermic reaction the temperature was increased to 30 ° C. 加热所述混合物,并在40°C搅拌1小时。 The mixture was heated and stirred at 40 ° C 1 hour. 其后,在压力下加热至130°C,并在该温度保持10小时。 Thereafter, heated to 130 ° C under pressure and maintained at that temperature for 10 hours. 在10小时内,连续加入16份固体100%氢氧化钠,并在130°C搅拌所述混合物。 Within 10 hours, continuously added 16 parts of 100% solid sodium hydroxide, and the mixture was stirred at 130 ° C. 热过滤得到的产物,用沸水充分洗涤并干燥。 The resulting product was filtered hot, washed well with boiling water and dried. 得到49.2份产物V,收率98%。 To give 49.2 parts of product V, 98% yield.

[0083] 该产物不溶于普通有机溶剂和水中,其在室温下的溶解度值低于0.1 %。 [0083] The product was insoluble in common organic solvents and in water, its solubility values ​​at room temperature less than 0.1%. 其表现出高于290°C的熔点,并具有下列通式: Which exhibits a higher melting point at 290 ° C, and having the following general formula:

[0084] [0084]

Figure CN101575408BD00102

[0085]其中 η 为10。 [0085] wherein η is 10.

[0086] 实施例7 [0086] Example 7

[0087] 通过使用哌啶代替实施例2中的吗啉,使用化合物V代替实施例2中的化合物III,生产化合物Va。 [0087] By using morpholine instead of piperidine in Example 2 using in place of Compound V Compound III in Example 2, production of the compound Va. 它是白色粉末,氯含量(Α0Χ) <0.01%。 It is white powder, the chlorine content (Α0Χ) <0.01%.

[0088] [0088]

Figure CN101575408BD00103

[0089] 实施例8 [0089] Example 8

[0090]使用 158 份N,N'-双-(2,2,6,6_ 四甲基_4_ 哌啶基)_1,6_ 己二胺(CAS Nr:61260-56-7)代替实施例1中的34.9份哌嗪,得到白色粉末的通式VI化合物。 [0090] Using 158 parts of N, N'- bis - (2,2,6,6_ _4_ tetramethyl piperidyl) hexamethylenediamine _1,6_ (CAS Nr: 61260-56-7) was used instead of 34.9 parts of piperazine, a compound of formula VI to give a white powder.

[0091] [0091]

Figure CN101575408BD00111

[0092] 实施例9 [0092] Example 9

[0093] 使用4-氨基-2,2,6,6-四甲基哌啶代替实施例3中的哌嗪,并使用通式VI化合物代替实施例3的通式III化合物,获得通式Via化合物。 [0093] using 4-piperazine in Example 3 2,2,6,6-tetramethyl-piperidine instead of embodiment, instead of using the compound of the formula VI compounds of formula III Example 3, the general formula Via compound.

[0094] [0094]

Figure CN101575408BD00112

[0095] 实施例10 [0095] Example 10

[0096] 使用通式VI化合物代替实施例2中的通式III化合物,获得通式VIb化合物。 Compounds of formula III Example 2 [0096] instead of the compound of the general formula VI embodiment, to obtain a compound of formula VIb.

[0097] [0097]

Figure CN101575408BD00113

[0098] 实施例11 [0098] Example 11

[0099] 使用168.8份1^ -双_(1,2,2,6,6-五甲基-4-哌啶基)_1,6-己二胺代替实施例1中34.9份哌嗪,获得为白色粉末的通式VII化合物。 [0099] Using 168.8 parts of 1 ^ - _ bis (1,2,2,6,6-pentamethyl-4-piperidyl) _1,6- Example 1 34.9 parts of piperazine was used instead of hexamethylenediamine, to obtain of the general formula VII compound as a white powder.

[0100] [0100]

Figure CN101575408BD00121

[0101] 实施例12 [0101] Example 12

[0102] 使用通式VII化合物代替实施例2中的通式III化合物,获得通式Vila化合物。 [0102] Using the compound of general formula VII used in Example 2 in the compound of formula III to give a compound of formula Vila.

[0103] [0103]

Figure CN101575408BD00122

[0104] 实施例13 [0104] Example 13

[0105] 使用4-氨基-2,2,6,6-四甲基哌啶代替实施例3中哌嗪,并使用通式VII化合物代替实施例3的通式III化合物,获得通式Vllb化合物。 [0105] using 4-amino-2,2,6,6-tetramethyl piperidine are used instead of the piperazine embodiment 3, and using instead of the compound of Formula VII compounds of formula III Example 3, to obtain a compound of formula Vllb .

[0106] [0106]

Figure CN101575408BD00123

[0107] 实施例14 [0107] Example 14

[0108] 使用叔辛胺代替实施例1中的吗啉,以97%收率获得通式VIII的产物。 [0108] Using t-octylamine was used instead of morpholine in Example 1, to obtain a 97% yield of product of formula VIII. 产物不溶 The insoluble product

于水和通常的有机溶剂中,并具有以下通式 Typically water and an organic solvent, and having the general formula

[0109] [0109]

Figure CN101575408BD00124

[0110]其中 η 为15。 [0110] wherein η is 15.

[0111] 实施例15[0112] 使用通式VIII的产物代替实施例2中的通式III产物,并使用哌啶代替实施例2中的吗啉,以97%收率获得通式Villa产物。 [0111] Example 15 [0112] Using general formula VIII in place of the product of Example III product of formula in Example 2, using piperidine instead of morpholine in Example Embodiment 2, in 97% yield to obtain the product of formula Villa. 产物不溶于水和通常的有机溶剂中,并具有以下通式。 The product insoluble in water and in common organic solvents, and has the following general formula.

[0113] [0113]

Figure CN101575408BD00131

[0114] 实施例16 [0114] Example 16

[0115] 使用六亚甲基二胺代替实施例6中的哌嗪,获得不溶于水和普通有机溶剂的通式IX产物,其中η是15。 [0115] Instead of using hexamethylenediamine piperazine in Example 6, to obtain insoluble in water and common organic solvents of the product of formula IX, where η is 15.

[0116] [0116]

Figure CN101575408BD00132

[0117] 实施例17 [0117] Example 17

[0118] 通过使用通式IX化合物代替实施例2中的通式III化合物,获得通式IXa的产物。 [0118] By using the compound of Formula IX in place of compounds of formula III described in Example 2, to obtain the product of formula IXa.

[0119] [0119]

Figure CN101575408BD00133

[0120] 可以通过在Stanton Redcroft装置中测量氧指数(根据ASTMD-2863),或通过应用UL-94标准(由"UnderwritersLaboratories " USA公开)测定自熄性能水平,其中UL-94标准提供了对塑料材料自熄性能水平的评估。 [0120] can (in accordance with ASTMD-2863), or by applying the UL-94 standards (published by the "UnderwritersLaboratories" USA) by measuring the oxygen index Stanton Redcroft apparatus measuring the level of self-extinguishing properties, wherein the UL-94 standard provides a plastic evaluation of the level of self-extinguishing properties of the material.

Claims (9)

1.无卤素含氮不溶于水的化合物,其由1,3,5-三嗪衍生物的低聚物或聚合物构成,并具有如下通式: 1. halogen-free compound is a nitrogen-containing water-insoluble, which oligomer or polymer consists of 1,3,5-triazine derivative, and having the general formula:
Figure CN101575408BC00021
或环中包含至少一个氮原子的杂环基团,该基团通过一个所述氮原子连接至三嗪环,R2是烷基或环烷基,R:是以下通式的哌嗪的二价基 Or a heterocyclic ring group containing at least one nitrogen atom, the group is attached to the triazine ring through a nitrogen atom of the, R2 is alkyl or cycloalkyl, R: is a piperazine of the general formula a divalent base
Figure CN101575408BC00022
η是2至30的整数,包括端值,m是2至6的整数,包括端值,和父片仏呢或乂'其中父和乂丨可以相同或不同; 所述化合物的制备方法包括步骤: a)在-10°C至+10°C温度范围,在pH值为5至7下,不使用任何有机溶剂,使氰尿酰卤与通式R2_NH2的胺或与环中包含氮原子的杂环化合物以摩尔比为1:1进行反应,以获得·2,6- 二氯-1,3,5-三嗪的4-氨基衍生物; b)不用分离,然后在热条件下,不使用任何有机溶剂,使中间悬浮液与通式H2N-(CH2)m_NH2的胺、与哌嗪反应,其中三嗪衍生物与胺和/或哌嗪之间的摩尔比等于1:1 ; c)通过在碱存在下,在90°C至150°C的温度下,使中间化合物与通式HXi的化合物反应,得到通式I的化合物。 η is an integer of 2 to 30, inclusive, m is an integer from 2 to 6, inclusive, and then the parent sheet or the qe Fo 'and qe Shu wherein the parent may be the same or different; the preparation of compounds comprises the step of : a) at -10 ° C to + 10 ° C temperature range, at a pH of 5-7, without using any organic solvent, cyanuric halide and an amine of formula R2_NH2 or contain a nitrogen atom in the ring the heterocyclic compound in a molar ratio of 1: 1 is reacted to obtain 4-amino-2,6-dichloro-1,3,5-triazine derivatives; b) without isolation, and then under thermal conditions, not any organic solvent, a suspension of the intermediate of the general formula H2N- (CH2) m_NH2 amine, reaction with piperazine, wherein the molar ratio between triazine derivative and amine and / or piperazine equal to 1: 1; c) in the presence of a base, at a temperature to 90 ° C and 150 ° C, reacting a compound of formula HXi the intermediate compound, to give a compound of general formula I. · ·
2.如权利要求1所述的化合物,其中所述方法的一个或多个步骤中加入表面活性剂。 2. The compound according to claim 1, wherein one or more steps of the method, a surfactant is added.
3.如权利要求1所述的化合物,其中所述方法的步骤c)在100°C至130°C的温度下进行。 The compound according to claim 1, wherein the process step c) is performed at a temperature between 100 ° C to 130 ° C.
4.一种生产权利要求1所述无卤素含氮不溶于水的化合物的方法,该方法通过在两个或三个步骤中氰尿酰卤与适当胺和/或杂环化合物的缩合进行。 Compound of claim 1 for producing a halogen-free nitrogen claim 4. A water-insoluble, by which cyanuric halide with the appropriate amine and condensation / or heterocyclic compounds is carried out in two or three steps.
5.如权利要求4所述的方法,包括步骤: a)在-10°C至+10°C温度范围,在pH值为5至7下,不使用任何有机溶剂,使氰尿酰卤与通式R2_NH2的胺或与环中包含氮原子的杂环化合物以摩尔比为1:1进行反应,以获得·2,6- 二氯-1,3,5-三嗪的4-氨基衍生物; b)不用分离,然后在热条件下,不使用任何有机溶剂,使中间悬浮液与通式H2N-(CH2)m_NH2的胺、与哌嗪反应,其中三嗪衍生物与胺和/或哌嗪之间的摩尔比等于1:1 ;c)通过在碱存在下,在90°C至150°C的温度下,使中间化合物与通式HX1的化合物反应,得到通式I的化合物。 5. The method according to claim 4, comprising the steps of: a) at -10 ° C to + 10 ° C temperature range, at a pH at 5-7, without using any organic solvent, cyanuric halide with R2_NH2 formula with an amine or a heterocyclic ring compound containing a nitrogen atom in a molar ratio of 1: 1 is reacted to obtain 4-amino-2,6-dichloro-1,3,5-triazine derivative ; b) without isolation and under hot conditions, without using any organic solvent, a suspension of the intermediate of the general formula H2N- (CH2) m_NH2 amine, reaction with piperazine, wherein the triazine derivative and amine and / or piperazine the molar ratio between triazine equal to 1: 1; c) in the presence of a base, at a temperature to 90 ° C and 150 ° C, reacting a compound of formula HX1 the intermediate compound, to give a compound of general formula I.
6.如权利要求5所述的方法,其中在一个或多个步骤中加入表面活性剂。 The method as claimed in claim 5, wherein the surfactant is added in one or more steps.
7.如权利要求5所述的方法,其中步骤c)在100°C至130°C的温度下进行。 7. The method according to claim 5, wherein step c) is performed at a temperature between 100 ° C to 130 ° C.
8.根据权利要求1所述无卤素含氮不溶于水的化合物的用途,其用作基于热塑性聚合物的自熄性聚合组合物中的阻燃剂。 8. The halogen-free nitrogen in claim 1 said water-insoluble use of a compound for use as a self-extinguishing polymeric compositions based on thermoplastic polymers flame retardant.
9.一种基于热塑性聚合物的自熄性聚合组合物,其包含权利要求1的无卤素含氮不溶于水的化合物。 A self-extinguishing polymeric compositions based on thermoplastic polymers, comprising as claimed in claim water-insoluble nitrogen-containing halogen-free compound 1. · ·
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