WO2020207235A1 - 一种聚甲醛复合材料及其制备方法和sebs在聚甲醛中作为消光剂的用途 - Google Patents

一种聚甲醛复合材料及其制备方法和sebs在聚甲醛中作为消光剂的用途 Download PDF

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WO2020207235A1
WO2020207235A1 PCT/CN2020/080613 CN2020080613W WO2020207235A1 WO 2020207235 A1 WO2020207235 A1 WO 2020207235A1 CN 2020080613 W CN2020080613 W CN 2020080613W WO 2020207235 A1 WO2020207235 A1 WO 2020207235A1
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sebs
polyoxymethylene
composite material
acid
parts
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PCT/CN2020/080613
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English (en)
French (fr)
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曹绍强
叶南飚
黄险波
陈锋
付学俊
禹权
丁超
彭忠泉
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金发科技股份有限公司
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Priority to JP2021559835A priority Critical patent/JP7324306B2/ja
Priority to EP20787634.3A priority patent/EP3943547A4/en
Priority to US17/601,713 priority patent/US20220195176A1/en
Publication of WO2020207235A1 publication Critical patent/WO2020207235A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L59/00—Compositions of polyacetals; Compositions of derivatives of polyacetals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L59/00—Compositions of polyacetals; Compositions of derivatives of polyacetals
    • C08L59/02—Polyacetals containing polyoxymethylene sequences only
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/005—Processes for mixing polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2359/00—Characterised by the use of polyacetals containing polyoxymethylene sequences only
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2451/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2217—Oxides; Hydroxides of metals of magnesium
    • C08K2003/222—Magnesia, i.e. magnesium oxide

Definitions

  • the invention relates to the technical field of polymer materials, in particular to a polyoxymethylene composite material and a preparation method thereof, and the use of SEBS as a matting agent in polyoxymethylene.
  • Polyoxymethylene is classified into oxymethylene homopolymer or oxymethylene copolymer. Among them, DuPont of the United States obtained a homopolymer of formaldehyde from formaldehyde polymerization around 1955. Polyoxymethylene is easy to crystallize, with a crystallinity of over 70%. The melting temperature of homopolyoxymethylene is about 180°C. It is another engineering plastic with excellent comprehensive properties after polyamide. It has high mechanical properties, such as strength, modulus, wear resistance, toughness, fatigue resistance and creep resistance, as well as excellent electrical insulation. , Solvent resistance and processability, is one of the five general engineering plastics.
  • the acetal polymer, polyoxymethylene is formed by the polymerization of formaldehyde, and it is also often called polyoxymethylene (POM).
  • POM polyoxymethylene
  • the preparation of polymers from formaldehyde had been studied as early as the 1920s, but it was not until 1959 that DuPont developed Delrin (Delrin) to produce thermally stable materials.
  • the homopolymer is made by anionic polymerization of very pure formaldehyde. Copolyformaldehyde was first developed and commercialized by Celanese in 1962 under the trade name "Celcon".
  • the catalyst mainly uses trioxymethylene and dioxane, in the catalyst (currently the main catalyst used is BF3 and its ether/butyl ether/ester complex, the catalyst has a suitable reaction rate and is easy to separate from the product after the reaction) and A polymer polymerized under the combined action of a molecular weight regulator (methylal MEAL).
  • a molecular weight regulator methylal MEAL
  • copolyoxymethylene has introduced CC chains in the molecular chain, so that when polyoxymethylene is decomposed, when the decomposition reaction reaches the CC bond, the chain degradation of formaldehyde is terminated, thereby improving the thermal stability of the material. More conducive to processing.
  • SEBS is a linear triblock copolymer with polystyrene as the terminal segment and ethylene-butene copolymer obtained by hydrogenation of polybutadiene as the middle elastic block.
  • SEBS is mainly used as a toughening agent in various thermoplastic resins, and it has also been modified for use.
  • Chinese patent 201210572164.2 discloses an ABS/POM alloy, which adds SEBS grafted maleic anhydride as a compatibilizer, but does not make in-depth explorations on other aspects of SEBS modification (such as acid modification or amine modification) to reduce Surface gloss of POM.
  • Chinese patent 201611151834.8 discloses a composite modified SEBS sheath material toughened by ethylene vinyl acetate copolymer, which uses a large amount of stearic acid to swell SEBS. After SEBS is fully swelled in stearic acid, oily SEBS is obtained, reducing ethylene acetic acid The agglomeration effect of ethylene copolymer and limestone in the system. The effect of modifying SEBS to bring low gloss to POM has not been documented.
  • the purpose of the present invention is to provide a polyoxymethylene composite material and a preparation method thereof, which has the advantage of low gloss.
  • Another object of the present invention is to provide the use of SEBS as a matting agent in polyoxymethylene.
  • a polyoxymethylene composite material characterized in that, in parts by weight, it comprises the following components:
  • SEBS is acid or amine modified.
  • the method of SEBS acid modification is bromination or acetylation.
  • a bromine or acetyl group is attached to the para position of the benzene ring, and then acidification or acetyl group oxidation is performed to obtain a carboxylic acid functional group.
  • the method of amine modification is to introduce a nitro group at the para position of the benzene ring in SEBS, and then convert the nitro group into an amino group through a reduction reaction.
  • SEBS is amine modified. Compared with acid modification, amine modified SEBS has a better matting effect.
  • acid-modified SEBS of the method 5g of the SEBS was dissolved in 50ml chloroform solution, followed by the addition of 0.2g of anhydrous FeCl 3, was slowly added dropwise with stirring a solution of bromine 2ml of the solution in the dark Stir at room temperature for 1 day, and precipitate the polymer with excess ethanol, then filter the solution, wash with acetone and water in turn, and then dry at 100°C to obtain brominated SEBS; dissolve 4g brominated SEBS in 15ml diphenyl ether, A mixture of 16 ml of diethyl phosphite, 0.08 g of Pd(dbac) 3 .CHCl 3 and 1.2 ml of triethylamine was added to the solution, and then refluxed at 155° C. under nitrogen for 2 days. The polymer was precipitated with ethanol/water solution (volume ratio 90/10), filtered and dried to obtain acid-modified SEBS.
  • Pd(dbac) 3 is a transition metal palladium catalyst, which can also be replaced by other catalysts.
  • the method of SEBS amine modification is: dissolve 5g of SEBS in 50ml of chloroform solution, and slowly drop a mixture of 60ml of nitric acid and 40ml of concentrated sulfuric acid into the solution under stirring conditions, and wait until the heat is completely dissipated. Then, stir at 70°C for 1 hour, then neutralize the excess acid with a 20% (w/w) NaOH solution, pour the chloroform layer into ethanol, precipitate the polymer, filter and dry to obtain the nitrated SEBS; Dissolve 4g of nitrated SEBS in 30ml of THF, dissolve 60g of stannous chloride in 60ml of HCl, and stir at 60°C to prepare a reduction mixture. The reduction mixture was added to the previous solution, and refluxed at 85°C for 3 hours, then neutralized with 10% (w/w) NaOH, precipitated the polymer with ethanol, filtered and dried to obtain an aminated SEBS.
  • SEBS acid modification and amine modification methods can be as above, but the above reagents, dosage, reaction conditions, etc. can be adjusted according to actual conditions.
  • the present invention utilizes the steric hindrance effect of the polystyrene segment in the SEBS on the polyoxymethylene, which has poor compatibility, and then uses acid or amine to modify the SEBS to further reduce the compatibility of the SEBS and the polyoxymethylene and reduce the polyoxymethylene molecular chain The ability of regular arrangement.
  • the incompatibility of the material itself will form a micro-rough effect on the surface of the material.
  • the reflection direction of the light will change and diffuse reflection will occur.
  • a low-gloss polyoxymethylene composite material is obtained.
  • the acid value of the SEBS is 5-15 (mg CH 3 ONa/g). Generally, SEBS has a certain acid value only after it is modified with acid or amine.
  • the acid value test method of SEBS adopts acid-base titration: the modified SEBS is titrated with 0.1 mol/L CH 3 ONa solution, and the acid value of SEBS is calculated by the end point of the titration. Take a certain amount of SEBS and add it to 50ml of chloroform. After it is completely dissolved, add bromphene blue indicator. After shaking, titrate with CH 3 ONa solution. When the solution turns from yellow to blue, stop the titration and calculate the acid value. "Mg CH 3 ONa/g" represents the milligrams of sodium methoxide required to neutralize 1 g of the sample.
  • the weight average molecular weight of the acid or amine SEBS of the present invention is 3,000-100,000.
  • the styrene segment content of the SEBS is 10-40%.
  • the presence of the styrene segment reduces the compatibility with POM due to the steric hindrance effect, thereby effectively reducing the gloss.
  • the compatibility is too poor and the matting performance can be improved, but it will lead to poor other properties of the POM composite.
  • the content of the styrene segment is too low, the matting effect is greatly reduced.
  • the impact strength is reduced by 15%, and the application is limited;
  • the matting performance is only 35% of the test example with a styrene segment content of about 37%.
  • the polyoxymethylene is at least one of homopolyoxymethylene or copolyoxymethylene; the melting index of the polyoxymethylene is 2-28 g/10min (190°C/2.16KG).
  • the formaldehyde absorbent is selected from at least one of magnesium oxide, magnesium hydroxide, aluminum oxide, and aluminum hydroxide.
  • Polyoxymethylene may decompose toxic formaldehyde gas during use, melt extrusion, molding, and injection molding. Add formaldehyde absorbent according to the situation.
  • auxiliary agent is selected from at least one of antioxidants, lubricants, heat stabilizers, and UV absorption additives.
  • the lubricant is selected from at least one of stearate lubricants, fatty acid lubricants, and stearate lubricants; the stearate lubricant is selected from calcium stearate, At least one of magnesium stearate and zinc stearate; the fatty acid lubricant is selected from at least one of fatty acids, fatty acid derivatives, and fatty acid esters; the stearate lubricant is selected It is selected from at least one of pentaerythritol stearate; preferably, the lubricant is selected from at least one of fatty acid lubricants and stearate lubricants.
  • Antioxidants include primary antioxidants or stabilizers (such as hindered phenols and/or secondary arylamines) and optional auxiliary antioxidants (such as phosphate esters and/or thioesters).
  • Suitable antioxidants include, for example, organic phosphates, such as tris(nonylphenyl) phosphite, tris(2,4-di-tert-butylphenyl) phosphite, bis(2,4-di-tert-butylbenzene) Base) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, etc., alkylated monohydric phenols or polyhydric phenols; polyhydric phenols and diene alkylation reaction products, such as tetra[methylene (3 ,5-Di-tert-butyl-4-hydroxyhydrocinnamate)] methane, etc.; butylated reaction product
  • Suitable heat stabilizers include, for example, organic phosphites such as triphenyl phosphite, tris(2,6-dimethylphenyl) phosphite, tris(mixed mono- and dinonylphenyl) phosphite , Etc.; phosphonates, such as dimethylphenylphosphonate, etc.; phosphates, such as trimethyl phosphate, etc.; or a combination containing at least one of the foregoing heat stabilizers.
  • organic phosphites such as triphenyl phosphite, tris(2,6-dimethylphenyl) phosphite, tris(mixed mono- and dinonylphenyl) phosphite , Etc.
  • phosphonates such as dimethylphenylphosphonate, etc.
  • phosphates such as trimethyl phosphate, etc.
  • Light stabilizers and/or ultraviolet light (UV) absorbing additives may be added.
  • Suitable light stabilizers include, for example, benzotriazoles, such as 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)-benzene Triazole and 2-hydroxy-4-n-octyloxybenzophenone, etc., also include triazine-based ultraviolet light absorbers or include at least one combination of the foregoing light stability.
  • Suitable UV absorbing additives include, for example, hydroxybenzophenones; hydroxybenzotriazoles; hydroxybenzotriazines; cyanoacrylates; oxalyl dianilides; benzoxazinones; 2-( 2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol (CYASORM 5411); 2-hydroxy-4-n-octyloxybenzophenone ( CYASORM 531); 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-(octyloxy)phenol (1164); 2,2'-(1,4-phenylene)bis(4H-3,1-benzoxazin-4-one)(CYASORM UV-3638); 1,3-bis[(2-cyano- 3,3-Diphenylacryloyl)oxy]-2,2-bis[[(2-cyano-3,3-diphenylacrylo
  • the preparation method of the above-mentioned polyoxymethylene composite material includes the following steps: adding polyoxymethylene, SEBS, auxiliary agent, and formaldehyde absorbent into a high-speed mixer and mixing uniformly, and then extruding and pelletizing the polyoxymethylene composite material by screw extrusion; ,
  • the temperature range of the screw is 120-200°C, and the speed is 250-500 rpm.
  • SEBS as a matting agent in polyformaldehyde includes the following components in parts by weight: 70-95 parts of polyformaldehyde; 5-20 parts of SEBS; among them, SEBS is acid or amine modified.
  • the present invention has the following beneficial effects:
  • the acid value is 5-15 (mg CH 3 ONa/g), which can reduce the gloss of polyformaldehyde.
  • acid-modified or amine-modified SEBS is added to the system.
  • This type of SEBS has poor compatibility with the polyoxymethylene resin matrix, which reduces the ability of polyoxymethylene molecular chains to be arranged regularly.
  • the incompatibility of the material itself will form a micro-rough effect on the surface of the material. When the incident light reaches the micro-rough surface, the reflection direction of the light will change and diffuse reflection will occur, resulting in a low-gloss POM composite material.
  • the raw materials used in the experiments of the examples and comparative examples are the following raw materials, but are not limited to the following raw materials:
  • Polyoxymethylene Longyu POM MC90, copolymerized POM, melt index: 9g/10min (190°C/2.16KG);
  • SEBS-A acid modification
  • SEBS raw material is Kraton G1650, self-made modification by acid modification method in the application manual, acid value is 10.2; mgCH 3 ONa/g, weight average molecular weight is about 70,000, and styrene segment content is about Is 30%;
  • SEBS-B Amine modification
  • SEBS raw material is Kraton G1652
  • the amine modification method in the application manual is self-made modification
  • the acid value is 5.1mgCH 3 ONa/g
  • the weight average molecular weight is about 50000
  • the styrene segment content is about 30%;
  • SEBS-C ordinary SEBS, SEBS 3151, without acid or amine modification, molecular weight is about 40,000, styrene segment content is about 32%;
  • SEBS-D S902
  • GMA grafting rate is 3%, without acid and amine modification.
  • SEBS-E acid modification, GMA grafting SEBS, self-made modification by acid modification method in the application manual, acid value is 9.7mgCH 3 ONa/g, weight average molecular weight is about 65000, styrene segment content is about 27% ;
  • Antioxidant hindered phenolic antioxidant IRGANOX 245/ hindered phenolic antioxidant RIANOX 1098;
  • the preparation method of the polyoxymethylene composite material of the embodiment and the comparative example includes the following steps: adding polyoxymethylene, SEBS, formaldehyde absorbent, and auxiliary agents into a high-speed mixer and mixing uniformly, and then extruding and granulating by screw to obtain polyoxymethylene composite Material; Among them, the temperature of the screw is 120/160/170/180/180/180/180/180/190°C, and the rotation speed is 300 rpm.
  • Gloss The degree of gloss is tested by a photoelectric gloss meter. Inject 10 pieces of 100mm*100mm*2.0mm square plates each, and use a photoelectric gloss meter (60° angle) to test the gloss of 10 square plates. take the average.
  • Table 1 The distribution ratio (weight parts) of each group of the embodiment and the comparative example and the performance test results
  • Example 3/5 and Comparative Example 1/2/3 that ordinary SEBS cannot effectively reduce the surface gloss of the polyoxymethylene composite material.
  • Example 3 It can be seen from Example 3 and Example 5 that the amine-modified SEBS has a better matting effect.

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Abstract

本发明公开了一种聚甲醛复合材料，按重量份计，包括以下组分：聚甲醛70-95份；SEBS 5-20份；其中，SEBS为酸或胺改性的。SEBS由于使用了酸或胺改性并且聚苯乙烯链段的存在，因为空间位阻效应，与聚甲醛的相容性降低，降低了POM分子链规整排列的能力，在注塑成制品或者样板时，材料本身的不相容会在材料表面形成微粗糙效果，当入射光到达微粗糙表面时，光的反射方向会发生改变从而出现漫反射，得到低光泽材料。

Description

一种聚甲醛复合材料及其制备方法和SEBS在聚甲醛中作为消光剂的用途 技术领域
本发明涉及高分子材料技术领域，特别是涉及一种聚甲醛复合材料及其制备方法和SEBS在聚甲醛中作为消光剂的用途。
背景技术
聚甲醛(POM)分为甲醛均聚物或者甲醛共聚物。其中，1955年前后美国杜邦公司由甲醛聚合得到甲醛的均聚物。聚甲醛很易结晶，结晶度70％以上。均聚甲醛的熔融温度为180℃左右。它是继聚酰胺之后又一种综合性能优良的工程塑料，具有高的力学性能，如强度、模量、耐磨性、韧性、耐疲劳性和抗蠕变性，还具有优良的电绝缘性、耐溶剂性和可加工性，是五大通用工程塑料之一。缩醛聚合物即聚甲醛是由甲醛聚合形成的，它也常称做聚氧亚甲基(POM)。由甲醛来制备聚合物早在20世纪20年代就被研究过，但是直到l959年杜邦开发出Delrin(戴林)以前尚来制得热稳定的材料。均聚物是用非常纯的甲醛经阴离子聚合制得。共聚甲醛是由美国塞拉尼斯(Celanese)于1962年首次开发并商品化的，商品名“Celcon”。主要是采用三聚甲醛和二氧五环，在催化剂(目前主要用的催化剂是BF3及其乙醚/丁醚/酯类的络合物，该催化剂反应速率合适，反应后容易与产物分离)和分子量调节剂(甲缩醛MEAL)的共同作用下聚合得到的聚合物。共聚甲醛相对于均聚甲醛，由于在分子链中引入了C-C链的存在，使得聚甲醛在分解时，当分解反应到C-C键时，终止甲醛的链式降解，从而提高材料的热稳定性，更利于加工。
SEBS是以聚苯乙烯为末端段，以聚丁二烯加氢得到的乙烯-丁烯共聚物为中间弹性嵌段的线性三嵌共聚物。SEBS主要用于各种热塑性树脂中作为增韧剂使用，也对其进行了改性使用。中国专利201210572164.2公开了一种ABS/POM合金，其加入SEBS接枝马来酸酐作为相容剂，但是没有对SEBS的其他方面改性(如酸改性或胺改性)作深入探索，以降低聚甲醛表面光泽度。中国专利201611151834.8公开了一种乙烯醋酸乙烯共聚物增韧的复合改性SEBS护套料，其使用大量硬脂酸来溶胀SEBS，待SEBS充分溶胀在硬脂酸中，得到油性SEBS，减少乙烯醋酸乙烯共聚物和石灰石等组份在体系中的团聚效应。通过改性SEBS来给POM带来低光泽度的效果没有被记载。
发明内容
本发明的目的在于，提供一种聚甲醛复合材料及其制备方法，其具有低光泽度的优点。
本发明的另一目的在于，提供SEBS在聚甲醛中作为消光剂的用途。
本发明是通过以下技术方案实现的：
一种聚甲醛复合材料，其特征在于，按重量份计，包括以下组分：
聚甲醛   70-95份；
SEBS     5-20份；
其中，SEBS为酸或胺改性的。
SEBS酸改性的方法为采用溴化或者乙酰化的方法，在苯环的对位接上一个溴或者乙酰基，然后再用酸进行酸化或者乙酰基团氧化得到羧酸官能团。
胺改性的方法为在SEBS中的苯环对位引入硝基，再通过还原反应将硝基转化成氨基。
优选的，SEBS为胺改性的。相对于酸改性，胺改性的SEBS消光效果更好。
具体的，SEBS酸改性的方法为：将5g的SEBS溶解于50ml三氯甲烷溶液中，随后向其中加入0.2g无水FeCl 3，搅拌条件下缓慢滴加2ml的溴溶液，溶液在黑暗条件下室温搅拌1天，并用过量乙醇沉淀聚合物，随后过滤溶液，依次采用丙酮和水冲洗，随后于100℃干燥，得到溴化的SEBS；将4g溴化的SEBS溶解在15ml二苯醚中，并将16ml亚磷酸二乙酯、0.08g Pd(dbac) 3.CHCl 3和1.2ml三乙胺的混合物添加到溶液中，然后在155℃氮气条件下回流2天。用乙醇/水溶液(体积比90/10)沉淀聚合物，过滤干燥，得到酸改性的SEBS。
Pd(dbac) 3为一种过渡金属钯催化剂，也可以使用其他催化剂取代。
具体的，SEBS胺改性的方法为：将5g的SEBS溶解于50ml三氯甲烷溶液中，在搅拌条件下，将60ml硝酸和40ml浓硫酸的混合液慢慢滴入溶液中，待热量完全散发后，于70℃搅拌1h，随后用20％(w/w)的NaOH溶液中和多余的酸，将三氯甲烷层倒入乙醇中，沉淀聚合物，过滤干燥，得到硝基化的SEBS；将4g硝基化的SEBS溶解于30ml THF中，将60g氯化亚锡溶解在60ml HCl中，60℃搅拌，制备还原混合物。将还原混合物加入前面的溶液中，并于85℃回流3小时，然后用10％(w/w)NaOH中和，用乙醇沉淀聚合物，过滤干燥，得到氨 基化的SEBS。
SEBS的酸改性、胺改性的方法总体思路可以如上，但是上述试剂、用量、反应条件等可以根据实际情况调整。
也可以是，先用GMA接枝SEBS，再对GMA支链进行酸改性。
本发明利用SEBS中聚苯乙烯链段对于聚甲醛的空间位阻效应，相容性差，再使用酸或胺改性SEBS，进一步降低了SEBS和聚甲醛的相容性，降低了聚甲醛分子链规整排列的能力，在注塑成制品或者样板时，材料本身的不相容会在材料表面形成微粗糙效果，当入射光到达微粗糙表面时，光的反射方向会发生改变，出现漫反射，从而得到低光泽的聚甲醛复合材料。
所述的SEBS的酸值为5-15(mg CH 3ONa/g)。一般的，SEBS只有用酸或者胺改性后才具有一定的酸值。
SEBS的酸值测试的方法采用酸碱滴定法：采用0.1mol/L的CH 3ONa溶液对改性过后的SEBS进行滴定，通过滴定终点计算SEBS的酸值。取一定量的SEBS，加入50ml三氯甲烷中，完全溶解之后，加入溴芬蓝指示剂，摇匀后，用CH 3ONa溶液进行滴定，当溶液由黄变蓝后停止滴定，计算酸值。“mg CH 3ONa/g”表示中和1g试样所需要的甲醇钠的毫克数。
本发明酸或胺SEBS的重均分子量为30000-100000。
优选的，所述的SEBS的苯乙烯链段含量为10-40％。苯乙烯链段的存在，由于空间位阻效应，使得与POM的相容性降低，从而有效的降低光泽度。试验过程中发现，当苯乙烯链段的含量太高，则相容性太差，消光性能能够提升，但是会导致聚甲醛复合材料的其他性能太差。当苯乙烯链段的含量太低，消光作用大打折扣。如实验中发现，当苯乙烯链段含量约为43％时，相比于苯乙烯链段含量约为37％的试验例，冲击强度下降了15％，应用受限；当苯乙烯链段含量约为8％时，消光性能仅为苯乙烯链段含量约为37％的试验例的35％。
所述的聚甲醛为均聚聚甲醛或者共聚聚甲醛中的至少一种；所述的聚甲醛的熔指为2～28g/10min(190℃/2.16KG)。
按重量份计，还包括0.5-1.2份的甲醛吸收剂；所述的甲醛吸收剂选自氧化镁、氢氧化镁、氧化铝、氢氧化铝中的至少一种。
聚甲醛有可能在使用、熔融挤出、模压、注塑过程中分解出有毒气体甲醛， 根据情况加入甲醛吸收剂。
按重量份计，还包括0.1-10份的助剂；所述的助剂选自抗氧剂、润滑剂、热稳定剂、UV吸收添加剂中的至少一种。
所述的润滑剂选自硬脂酸盐类润滑剂、脂肪酸类润滑剂、硬脂酸酯类润滑剂中的至少一种；所述的硬脂酸盐类润滑剂选自硬脂酸钙、硬脂酸镁、硬脂酸锌中的至少一种；所述的脂肪酸类润滑剂选自脂肪酸、脂肪酸衍生物、脂肪酸酯中的至少一种；所述的硬脂酸酯类润滑剂选自季戊四醇硬脂酸酯中的至少一种；优选的，所述的润滑剂选自脂肪酸类润滑剂、硬脂酸酯类润滑剂中的至少一种。
抗氧剂包括主抗氧剂或稳定剂(如受阻酚和/或仲芳基胺)和任选的辅助抗氧化剂(例如磷酸酯和/或硫酯)。合适的抗氧化剂包括例如有机磷酸酯，例如亚磷酸三(壬基苯基)酯、亚磷酸三(2,4-二叔丁基苯基)酯、二(2,4-二叔丁基苯基)季戊四醇二亚磷酸酯、二硬脂基季戊四醇二亚磷酸酯等等，烷基化的一元酚或多元酚；多元酚与二烯的烷基化反应产物，例如四[亚甲基(3,5-二叔丁基-4-羟基氢化肉桂酸酯)]甲烷等等；对甲酚或二环戊二烯的丁基化反应产物；烷基化氢醌；羟基化硫代二苯醚；烷叉双酚；苄基化合物；β-(3,5-二叔丁基-4-羟基苯基)-丙酸与一元醇或多元醇的酯；β-(5-叔丁基-4-羟基-3-甲基苯基)-丙酸与一元醇或多元醇的酯；硫烷基或硫芳基化合物的酯，例如二硬脂基硫代丙酸酯、二月桂基硫代丙酸酯、二(十三烷基)硫代丙酸酯、十八烷基-3-(3,5-二叔丁基-4-羟基苯基)丙酸酯、季戊四醇-四[3-(3,5-二叔丁基-4-羟基苯基)]丙酸酯等等；β-(3,5-二叔丁基-4-羟基苯基)-丙酸的酰胺等等；或者包含至少一种前述抗氧化剂的组合。
合适的热稳定剂包括例如有机亚磷酸酯，例如亚磷酸三苯酯、亚磷酸三(2,6-二甲基苯基)酯、亚磷酸三(混合的单和二壬基苯基)酯，等等；膦酸酯，例如二甲基苯膦酸酯等等；磷酸酯，例如磷酸三甲基酯等等；或者包含至少一种前述热稳定剂的组合。
可以添加光稳定剂和/或紫外光(UV)吸收添加剂。合适的光稳定剂包括例如苯并三唑类，例如2-(2-羟基-5-甲基苯基)苯并三唑、2-(2-羟基-5-叔辛基苯基)-苯并三唑和2-羟基-4-正辛氧基二苯甲酮等等，也包括三嗪类的紫外光吸收剂或者包含至少一种前述光稳定的组合。
合适的UV吸收添加剂包括例如羟基二苯甲酮类；羟基苯并三唑类；羟基苯 并三嗪类；氰基丙烯酸酯类；草酰二苯胺类；苯并噁嗪酮类；2-(2H-苯并三唑-2-基)-4-(1,1,3,3-四甲基丁基)苯酚(CYASORM 5411)；2-羟基-4-正辛氧基二苯甲酮(CYASORM 531)；2-[4,6-双(2,4-二甲基苯基)-1,3,5-三嗪-2-基]-5-(辛氧基)苯酚(1164)；2,2’-(1,4-亚苯基)双(4H-3,1-苯并噁嗪-4-酮)(CYASORM UV-3638)；1,3-双[(2-氰基-3,3-二苯基丙烯酰基)氧基]-2，2-双[[(2-氰基-3,3-二苯基丙烯酰基)氧基]甲基]丙烷(UVINUL 3030)；纳米尺寸的无机材料，例如氧化钛、氧化铈和氧化锌，所有这些的粒度小于100nm，或类似物；或含至少一种前述UV吸收剂的组合。
上述的聚甲醛复合材料的制备方法，包括以下步骤：将聚甲醛、SEBS、助剂、甲醛吸收剂加入高速混料机中混合均匀，再通过螺杆挤出、造粒得到聚甲醛复合材料；其中，螺杆的温度范围是120-200℃，转速为250-500转/分。
SEBS在聚甲醛中作为消光剂的用途，按重量份计，包括以下组分：聚甲醛70-95份；SEBS 5-20份；其中，SEBS为酸或胺改性的。
与现有技术相比，本发明具有如下有益效果：
本发明通过在聚甲醛中加入用酸或胺改性的SEBS，酸值为5-15(mg CH 3ONa/g)，能够降低聚甲醛的光泽度。具体是在体系中加入了使用酸改性或胺改性的SEBS，此类SEBS与聚甲醛树脂基体的相容性变差，降低了聚甲醛分子链规整排列的能力，在注塑成制品或者样板时，材料本身的不相容会在材料表面形成微粗糙效果，当入射光到达微粗糙表面时，光的反射方向会发生改变，出现漫反射，从而得到低光泽的聚甲醛复合材料。
具体实施方式
下面通过具体实施方式来进一步说明本发明，以下实施例为本发明较能体现发明思路的实施方式，但是本发明的实施方式并不受下述实施例的限制。
实施例与对比例实验所用的原料为以下原料，但不限于以下原料：
聚甲醛：龙宇POM MC90，共聚POM，熔指：9g/10min(190℃/2.16KG)；
SEBS-A：酸改性，SEBS原料为科腾G1650，应用说明书中酸改性方法自制改性，酸值为10.2；mgCH 3ONa/g，重均分子量约为70000，苯乙烯链段含量约为30％；
SEBS-B：胺改性，SEBS原料为科腾G1652，应用说明书中胺改性方法自制改性，酸值为5.1mgCH 3ONa/g，重均分子量约为50000，苯乙烯链段含量约为 30％；
SEBS-C：普通SEBS，SEBS 3151，没有进行酸、胺改性，分子量约为40000，苯乙烯链段含量约为32％；
SEBS-D：S902，GMA接枝率3％，没有进行酸、胺改性。
SEBS-E：酸改性，GMA接枝SEBS，应用说明书中酸改性方法自制改性，酸值为9.7mgCH 3ONa/g，重均分子量约为65000，苯乙烯链段含量约为27％；
氧化镁：KYOWAMAG 150；
抗氧剂：受阻酚类抗氧剂IRGANOX 245/受阻酚类抗氧剂RIANOX 1098；
实施例和对比例聚甲醛复合材料的制备方法，包括以下步骤：将聚甲醛、SEBS、甲醛吸收剂、助剂加入高速混料机中混合均匀，再通过螺杆挤出、造粒得到聚甲醛复合材料；其中，螺杆的温度120/160/170/180/180/180/180/180/180/190℃，转速为300转/分。
各项性能测试方法：
(1)光泽度：光泽度的大小通过光电光泽度仪进行测试，注塑100mm*100mm*2.0mm方板各10块，采用光电光泽度仪(60°角)测试10个方板的光泽度，取平均值。
表1：实施例和对比例各组分配比(重量份)及各性能测试结果
Figure PCTCN2020080613-appb-000001
从实施例1-4和对比例3可以看出，用酸改性的SEBS加入量增加，聚甲醛 复合材料表面的光泽度随之降低。
从实施例3/5、对比例1/2/3可以看出，普通的SEBS是不能有效降低聚甲醛复合材料的表面光泽度的。
从实施例3和实施例5可以看出，胺改性的SEBS消光效果较好。

Claims (11)

  1. 一种聚甲醛复合材料，其特征在于，按重量份计，包括以下组分：
    聚甲醛           70-95份；
    SEBS             5-20份；
    其中，SEBS为酸或胺改性的。
  2. 根据权利要求1所述的聚甲醛复合材料，其特征在于，所述的酸改性的SEBS含有羧酸官能团；所述的胺改性的SEBS含有氨基。
  3. 根据权利要求2所述的聚甲醛复合材料，其特征在于，所述的SEBS的酸值为5-15(mg CH 3ONa/g)。
  4. 根据权利要求1所述的聚甲醛复合材料，其特征在于，所述的酸改性为采用溴化或者乙酰化的方法，在苯环的对位接上一个溴或者乙酰基，然后再用酸进行酸化或者乙酰基团氧化得到羧酸官能团；所述的胺改性的方法为在SEBS中的苯环对位引入硝基，再通过还原反应将硝基转化成氨基；优选的，SEBS为胺改性的。
  5. 根据权利要求4所述的聚甲醛复合材料，其特征在于，先用GMA接枝SEBS，再对GMA支链进行酸改性。
  6. 根据权利要求1-3任一项所述的聚甲醛复合材料，其特征在于，所述的SEBS的重均分子量为30000-100000，其中苯乙烯链段占总链段分子量的10-40％。
  7. 根据权利要求1所述的聚甲醛复合材料，其特征在于，所述的聚甲醛为均聚聚甲醛或者共聚聚甲醛中的至少一种；所述的聚甲醛的熔指为2～28g/10min(190℃/2.16KG)。
  8. 根据权利要求1所述的聚甲醛复合材料，其特征在于，按重量份计，还包括0.5-1.2份的甲醛吸收剂；所述的甲醛吸收剂选自氧化镁、氢氧化镁、氧化铝、氢氧化铝中的至少一种。
  9. 根据权利要求1所述的聚甲醛复合材料，其特征在于，按重量份计，还包括0.1-10份的助剂；所述的助剂选自抗氧剂、润滑剂、热稳定剂、UV吸收添加剂中的至少一种。
  10. 权利要求9所述的聚甲醛复合材料的制备方法，其特征在于，包括以下步骤：将聚甲醛、SEBS、助剂加入高速混料机中混合均匀，再通过螺杆挤出、造粒得到聚甲醛复合材料；其中，螺杆的温度范围是120-200℃，转速为250-500转/分。
  11. SEBS在聚甲醛中作为消光剂的用途，其特征在于，按重量份计，包括以下组分：聚甲醛70-95份；SEBS 5-20份；其中，SEBS为酸或胺改性的。
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