CN1252410A - 用于快速模型研究的共聚物 - Google Patents
用于快速模型研究的共聚物 Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/04—Acids; Metal salts or ammonium salts thereof
- C08F120/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
- B29C41/003—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor characterised by the choice of material
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Abstract
本发明涉及平均粒度为6～50μm的、具有窄粒度分布的球形甲基丙烯酸甲酯共聚物,及其生产方法。本发明还涉及用这种球形共聚物通过激光熔结生产三维模型。
Description
本发明涉及平均粒度为6～50μm的、具有窄粒度分布的球形甲基丙烯酸甲酯共聚物，及其生产方法。本发明还涉及用这种球形共聚物通过激光熔结生产三维模型。
术语“激光熔结”意指一种快速模型研究(rapid prototyping)的方法，其中，将限定粉状材料的浇注体加热，以及，借助激光束的作用在限定座标之间进行熔结，该法优选采用程序控制。使用“快速模型研究”这个术语概括制造现称为三维模型的计算机控制辅助的自动化方法。
例如，专利说明书DE-C 19701078中所叙述的方法。在该方法中，熔结低熔点金属是，采用借助快速模型研究的设备生产三维模型的工艺过程的一部分。熔点低于200℃的低熔点金属或金属合金以既不含有塑料材料粘合剂又不含有金属粘合剂的金属粉末或金属箔的形式使用。所使用的激光束的能量依所使用的金属或金属合金的熔点进行调节。
还已知用塑料粉末进行激光熔结(A.Gebhardt，“RapidPrototyping”，Carl Hanser Verlag，Munich，Vienna 1996，page115～116)。该方法用于生产塑料模型以及制造陶瓷铸塑模具用的阳料坯(positive preform)。基于聚甲基丙烯酸酯的良好光学性质和机械性质，其是相当适于激光熔结的塑料材料。
已知塑料粉末的一个缺点是其流动性差。该缺点通过使用流动改进剂仅仅能够得到部分减轻。由于塑料粉末流动行为不良，所以难以在激光熔结设备中进行输送。
在生产陶瓷用阳料坯过程中还存在如下其它问题。虽能够熔结诸如聚苯乙烯等研磨过的聚合物，但料坯的表面质量并不完全令人满意。聚合物料坯随后被陶瓷材料围绕，其在高温下燃烧而赋于强度。在该步骤中，聚合物材料被挥发了。完全挥发是理想的。然而，基于使用流动改进剂，使大多数聚合物粉末不能靠燃烧除去，而留下残渣。
通过使用球形聚合物珠粒料进行激光熔结能够避免这些缺点。
采用分散聚合的方法能够生产诸如聚甲基丙烯酸甲酯等的粒度为0.5～10μm的球形聚合物珠粒料形式的均聚物。例如，EP-A 610522叙述了一种适宜的方法。在分散聚合中，使用可溶解所用单体而不溶解所形成聚合物的溶剂。一般说，分散聚合提供高收率的、粒度分布窄的、具有适于激光熔结的低分子量的球形聚合物珠粒料。然而，现已表明，难以生产较大粒子。该工艺的另一个显著特征是，粒度分布随着粒度增加而显著变得较宽。
从EP-A 610522可知，与使甲基丙烯酸甲酯进行均聚制得的产物相比，使甲基丙烯酸甲酯与作为共聚单体的苯乙烯进行分散聚合，得到了粒度分布显著变宽的较小微粒。按照US-A 4614708，通过分散聚合所制得的甲基丙烯酸甲酯和其它甲基丙烯酸酯的球形共聚物粒度最高为5μm。粒度小于5μm的聚合物珠粒料较不适于激光熔结，因为其流动性差，且有显著的成灰倾向。按照EP-A 584407，通过使甲基丙烯酸甲酯与作为共聚单体的丙烯酸或甲基丙烯酸进行分散聚合，能够制得包含甲基丙烯酸甲酯单元的、粒度为6μm的、粒度分布窄的球形聚合物珠粒料。然而，这些产品难以熔融，所以，对于激光熔结来说，同样仅仅具有有限的适用性。
能够采用悬浮聚合制得粒度约10～200μm的珠状聚合物。将术语“悬浮聚合”理解为，意指一种方法，在该方法中，将含有可溶于单体的引发剂的单体或含这样的单体的混合物，破碎形成滴状，其可能以具有小固体颗粒的混合物的形式存在于基本上与单体不溶混的含有分散剂的相中，以及经升温同时进行搅拌使其固化。关于悬浮聚合的更详细的资料载于，例如，C.E.Schildknecht(编者)，“聚合物制法”(Polymer Processes)，Interscience Publishers，纽约，1956，第69～109页。
悬浮聚合的一种缺点是所制得的聚合物珠粒料的粒度分布宽。在激光熔结过程中，粒度分布宽会致使质量再现性差和能导致不均匀。所以，在聚合之后，必须将珠粒料过筛，以便得到适于激光熔结的筛分。悬浮聚合的另一个缺点是，必须使用相当数量的分子量调节剂，才能制得具有适于激光熔结的足够低的分子量的聚合物。使用这样大量的分子量调节剂对聚合速率和收率均有负面影响。
现已发现，通过使甲基丙烯酸甲酯与至少一种选自甲基丙烯酸C2～10烷基酯的共聚单体，任选与至少一种硅烷进行分散共聚，制得了具有激光熔结所必需的粒度以及粒度分布窄的球形聚合物珠粒料。
平均粒度(φ)和粒度分布通过光学分析进行测定。使用体积分布的90％值(φ(90))与10％值(φ(10))的比确定所制得的球形共聚物的粒度分布的宽度。在本发明意义上，粒度分布窄意指φ(90)/φ(10)小于2.0，优选φ(90)/φ(10)小于1.5。
本发明涉及一种球形甲基丙烯酸甲酯共聚物，其平均粒度为6～50um，具有如上述限定的窄粒度分布，包含，按共聚物重量计：
a)90～50％(重量)，优选90～60％(重量)，最优选80～60％(重量)甲基丙烯酸甲酯单元，和
b)10～50％(重量)，优选10～40％(重量)，最优选20～40％(重量)至少一种甲基丙烯酸C2～C10烷基酯单元。
本发明还涉及一种制备按照本发明的甲基丙烯酸甲酯共聚物的方法，其中采用引发剂通过分散聚合使下述组成的单体混合物聚合：
a)90～50％(重量)，优选90～60％(重量)，最优选80～60％(重量)甲基丙烯酸甲酯，和
b)10～50％(重量)，优选10～40％(重量)，最优选20～40％(重量)至少一种甲基丙烯酸C2～C10烷基酯。
本发明还涉及使用按照本发明的共聚物作为激光熔结用的熔结材料。
能够将按照EP-A 417539的甲基丙烯酸C2～C10酯或硅烷单体用作按照本发明的含有C2～C10烷基自由基的甲基丙烯酸酯。优选甲基丙烯酸的C2～C8酯；特别优选甲基丙烯酸的C2～C4酯。适宜的例子包括甲基丙烯酸乙酯、甲基丙烯酸正丙酯、甲基丙烯酸异丙酯、甲基丙烯酸正丁酯、甲基丙烯酸异丁酯、甲基丙烯酸正己酯、甲基丙烯酸2-乙基己酯、甲基丙烯酸正辛酯、甲基丙烯酸正癸酯、甲基丙烯酸甲氧基乙酯、甲基丙烯酸甲氧基丁酯、单甲基丙烯酸三乙二醇酯、甲基丙烯酰氧丙基三甲氧基硅烷和甲基丙烯酰氧丙基三乙氧基硅烷。优选甲基丙烯酸乙酯、甲基丙烯酸正丙酯、甲基丙烯酸异丙酯、甲基丙烯酸正丁酯和甲基丙烯酸异丁酯。
在按照本发明的生产甲基丙烯酸甲酯共聚物的方法中，采用引发剂使上述单体在溶剂中进行共聚。
适宜的溶剂包括诸如二噁烷、丙酮、乙腈、二甲基甲酰胺和醇等非水溶剂。优选低分子量醇，特别是甲醇、乙醇、正丙醇、异丙醇、正丁醇、异丁醇和叔丁醇。不同溶剂的混合物也是很适宜的，特别是不同醇的混合物。醇也可以含有至多50％(重量)水，优选含有至多25％(重量)水。在使用溶剂混合物时，能够组合使用非极性溶剂，特别是诸如己烷和庚烷等烃，其比例为至多50％(重量)。
单体混合物与溶剂的比例为1∶1至1∶20，优选为1∶3至1∶10。
按照本发明方法优选在高分子量分散剂存在下实施(平均分子量(Mw)10000至1000000g/mol)。
溶解于所用溶剂的天然和合成大分子化合物适于作高分子量分散剂。其例子包括纤维素衍生物，例如甲基纤维素、乙基纤维素或羟丙基纤维素、聚醋酸乙烯，部分皂化的聚醋酸乙烯、聚乙烯吡咯烷酮、和乙烯基吡咯烷酮和醋酸乙烯的共聚物，以及苯乙烯和马来酸酐的共聚物。优选聚乙烯吡咯烷酮。高分子量分散剂的含量为0.1～20％(重量)，优选0.2～10％(重量)，相对于溶剂计。
除了分散剂之外，还能使用离子和非离子表面活性剂。适宜的表面活性剂的例子包括磺基丁二酸钠、甲基三辛酰铵氯化物或乙氧基化的壬基酚。表面活性剂用量能为0.1～2％(重量)，相对于溶剂计。
适用于按照本发明方法的引发剂是在温度升高时形成自由基的化合物。其例子包括：环氧化合物，如过氧化二苯酰、过氧化二月桂酰、过氧化双-对-氯苯酰、过氧二碳酸二环己酯和叔戊基过氧-2-乙基己烷，以及偶氮化合物，如2，2′-偶氮双(异丁腈)和2，2′-偶氮双(2-甲基异丁腈)。只要极性介质含有至少5％(重量)水，过氧二硫酸钠也是适宜的。
通式I、II或III的脂族过氧化酯也是十分适宜的，
式中：
R1是含有2～20个碳原子的烷基或环烷基，
R2是含有4～12个碳原子的支链烷基，
L是含有2～20个碳原子的亚烷基或亚环烷基。
通式I的酯族过氧化酯的例子包括过氧乙酸叔丁酯、过氧异丁酸叔丁酯、过氧新戊酸叔丁酯、过氧辛酸叔丁酯、过氧-2-乙基己酸叔丁酯、过氧新癸酸叔丁酯、过氧新戊酸叔戊酯、过氧辛酸叔戊酯、过氧-2-乙基己酸叔戊酯和过氧新癸酸叔戊酯。
通式II的脂族过氧化酯的例子包括2，5-双(2-乙基-己酰过氧)-2，5-二甲基己烷，2，5-二新戊酰-2，5-二甲基己烷和2，5-双(2-新癸酰过氧)-2，5二甲基己烷。
通式III的脂族过氧化酯的例子包括过氧壬二酸二叔丁酯和过氧壬二酸二叔戊酯。
引发剂的用量一般为0.05～6.0％(重量)，优选0.2～4.0％(重量)，相对于单体混合物计。
聚合温度取决于前述引发剂的分解温度和溶剂的沸点，一般为50～150℃，优选为55～120℃。有利的是，在溶剂沸点下进行聚合，及有利的是，在聚合期间进行搅拌。聚合时间一般为几小时，例如2～30小时。
通过过滤能够把本发明共聚物从反应混合物中分离出来，或者，特别有利的是，能借助离心分离或倾析设备通过沉降将其分离出来。
比较例1～8
在4升装有网眼搅拌器的反应器中将2340g甲醇、180g聚乙烯吡咯烷酮K 30(Mw＝55000g/mol)和300g由甲基丙烯酸甲酯和任选不同共聚单体(表1)组成的单体混合物混合成均匀溶液。在氮气氛围下将所得溶液加热至55℃，历时1小时，搅拌速度为100rpm，再将6g2，2′-偶氮双(异丁腈)在165g甲醇中的溶液加到反应器中。将聚合混合物在55℃ 100rpm下再搅拌20小时。以后将最终聚合物分散体冷却至室温，通过沉降分离出聚合物珠粒料。所制得的聚合物珠粒料的粒度列于表1。
表1：用作比较例的甲基丙烯酸甲酯共聚物
EtMA＝甲基丙烯酸乙酯；n-BuMA＝甲基丙烯酸正丁酯；EtHexMA＝甲基丙烯酸乙基己酯；DodMA＝甲基丙烯酸十二烷基酯；StMA＝甲基丙烯酸十八烷基酯
| 比较例 | MMA[％(重量)] | 共聚单体 | 共聚单体[％(重量)] | φ[μm] | φ(10)[μm] | φ(90)[μm] | φ(90)/φ(10) |
| 1 | 100 | 0 | 4.37 | 4.03 | 4.78 | 1.19 | |
| 2 | 95 | EtMA | 5 | 4.36 | 4.02 | 4.77 | 1.19 |
| 3 | 95 | n-BuMA | 5 | 5.40 | 4.76 | 6.04 | 1.26 |
| 4 | 95 | EtHexMA | 5 | 4.71 | 4.16 | 4.86 | 1.17 |
| 5 | 95 | DodMA | 5 | 4.96 | 4.46 | 5.36 | 1.20 |
| 6 | 95 | StMA | 5 | 3.71 | 3.38 | 3.94 | 1.17 |
| 7 | 75 | DodMA | 25 | 3.08 | 2.73 | 3.40 | 1.24 |
| 8 | 75 | StMA | 25 | 2.51 | 2.06 | 3.13 | 1.52 |
实例1～12
以和比较例相同的方式进行聚合和加工。所使用的单体混合物和所制得的聚合物珠粒料的粒度列于表2。
表2：按照本发明的甲基丙烯酸甲酯共聚物
EtMA＝甲基丙烯酸乙酯；n-BuMA＝甲基丙烯酸正丁酯；EtHexMA＝甲基丙烯酸乙基己酯
| 实例 | MMA[％(重量)] | 共聚单体 | [％(重量)] | φ[μm] | φ(10)[μm] | φ(90)[μm] | φ(90)/φ(10) |
| 1 | 80 | EtMA | 20 | 6.64 | 6.06 | 6.91 | 1.14 |
| 2 | 75 | EtMA | 25 | 8.48 | 7.62 | 9.14 | 1.20 |
| 3 | 70 | EtMA | 30 | 12.24 | 11.37 | 13.42 | 1.18 |
| 5 | 80 | n-BuMA | 20 | 8.54 | 7.79 | 9.10 | 1.17 |
| 6 | 75 | n-BuMA | 25 | 10.12 | 9.24 | 11.27 | 1.22 |
| 7 | 70 | n-BuMA | 30 | 12.03 | 10.31 | 14.05 | 1.36 |
| 8 | 60 | n-BuMA | 40 | 25.49 | 20.37 | 28.97 | 1.42 |
| 9 | 50 | n-BuMA | 50 | 35.77 | 25.11 | 49.54 | 1.97 |
| 10 | 80 | EtHexMA | 20 | 7.59 | 6.84 | 7.78 | 1.14 |
| 11 | 75 | EtHexMA | 25 | 6.64 | 6.10 | 7.25 | 1.19 |
| 12 | 70 | EtHexMA | 30 | 6.47 | 5.85 | 6.95 | 1.19 |
采用Soft Imaging Systems公司提供的SIS光学分析仪，进行在实例和比较例中所制得的产物的粒子直径和粒度分布的测定。使用水作为分散介质。测定在暗区中以放大倍数1180进行，焦点调节在最大的最终粒子。使用投影面积作为粒子的一个特征，其由当量直径的球体面积计算。测定形状因数，作为另一个参数。在评价时，可借助该形状因数区分聚集体等。每个样品至少测定2000个粒子，以便得到有意义的统计结果。从所测定的粒径分布求出平均粒径(φ)。以及体积分布的10％值(φ(10))和90％值(φ(90))。图1示出实例1的结果。
Claims (8)
1.球形甲基丙烯酸甲酯共聚物，其结构单元包括：
a)90～50％甲基丙烯酸甲酯，和
b)10～50％至少一种甲基丙烯酸C2～10烷基酯；所述百分数，两种情况，均相对于所述共聚物的重量计；所述材料的形状为基本呈球形的颗粒，其体积平均粒度为6～50微米，粒度分布宽度为2.0以下。
2.按照权利要求1的球形甲基丙烯酸甲酯共聚物，其中所述a)的存在量为90～60％，而所述b)的存在量为10～40％。
3.按照权利要求1的球形甲基丙烯酸甲酯共聚物，其中所述a)的存在量为80～60％，而所述b)的存在量为20～40％。
4.按照权利要求1的球形甲基丙烯酸甲酯共聚物，其中所述粒度分布宽度小于1.5。
5.一种制造权利要求1的球形甲基丙烯酸甲酯共聚物的方法，包括在引发剂存在下使包含下述的单体混合物进行分散聚合：
a)90～50％甲基丙烯酸甲酯，和
b)10～50％至少一种甲基丙烯酸C2～10烷基酯，所述百分数，两种情况，均相对于所述混合物重量计。
6.权利要求5的方法，其中聚合在高分子量分散剂存在下进行。
7.权利要求5的方法，其中所述引发剂的存在量为0.05～6％，相对于单体混合物重量计。
8.按照权利要求1的共聚物用作借助激光熔结制备三维模型的熔结材料。
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| DE3265276D1 (en) * | 1981-11-23 | 1985-09-12 | Agfa Gevaert Nv | Method for the preparation of stable aqueous dispersions of polymer beads and the use of these dispersions in photographic elements |
| DE69225222T2 (de) * | 1992-08-27 | 1998-10-29 | Agfa Gevaert Nv | Bildempfangsmaterial zur Verwendung in einem Silbersalz-Diffusionsübertragungsverfahren |
| DE69324564T2 (de) * | 1993-02-08 | 1999-11-25 | Imation Corp | Photographisches Silberhalogenidmaterial, das monodisperse Polymerteilchen enthält |
-
1998
- 1998-10-23 DE DE19848896A patent/DE19848896A1/de not_active Withdrawn
-
1999
- 1999-10-12 EP EP99119969A patent/EP0995763A3/de not_active Withdrawn
- 1999-10-14 US US09/418,298 patent/US6143852A/en not_active Expired - Fee Related
- 1999-10-21 JP JP11299418A patent/JP2000128939A/ja active Pending
- 1999-10-22 KR KR1019990045937A patent/KR20000029244A/ko not_active Application Discontinuation
- 1999-10-22 CN CN99123325A patent/CN1252410A/zh active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| US6143852A (en) | 2000-11-07 |
| DE19848896A1 (de) | 2000-04-27 |
| JP2000128939A (ja) | 2000-05-09 |
| KR20000029244A (ko) | 2000-05-25 |
| EP0995763A3 (de) | 2000-05-24 |
| EP0995763A2 (de) | 2000-04-26 |
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