CN1208374C - 无空洞的聚合物颗粒 - Google Patents
无空洞的聚合物颗粒 Download PDFInfo
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- CN1208374C CN1208374C CNB998047953A CN99804795A CN1208374C CN 1208374 C CN1208374 C CN 1208374C CN B998047953 A CNB998047953 A CN B998047953A CN 99804795 A CN99804795 A CN 99804795A CN 1208374 C CN1208374 C CN 1208374C
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- polycarbonate
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- 229920000642 polymer Polymers 0.000 title claims abstract description 15
- 239000008187 granular material Substances 0.000 title abstract description 4
- 238000000034 method Methods 0.000 claims abstract description 14
- 230000009477 glass transition Effects 0.000 claims abstract description 3
- 229920000515 polycarbonate Polymers 0.000 claims description 22
- 239000004417 polycarbonate Substances 0.000 claims description 22
- 238000005453 pelletization Methods 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 11
- 239000011324 bead Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000008188 pellet Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 4
- 229920001169 thermoplastic Polymers 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- 239000011800 void material Substances 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000005587 carbonate group Chemical group 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- -1 polyphenylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
-
- 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
- C08J3/12—Powdering or granulating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/02—Making granules by dividing preformed material
- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/12—Making granules characterised by structure or composition
-
- 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
- B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
- B29C35/16—Cooling
- B29C2035/1616—Cooling using liquids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2069/00—Use of PC, i.e. polycarbonates or derivatives thereof, as moulding material
-
- 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
- C08J2369/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
本发明涉及一种制备无空洞的聚合物颗粒的方法。所述的聚合物在被挤出后、在≤50℃到刚好在玻璃化转变温度之上的温度的温度下被冷却,然后将其切粒。
Description
本申请涉及生产无空洞的聚合物颗粒的方法,其中,挤出后的聚合物在被切粒前以≤50℃/秒的速度冷却到刚好在玻璃化转变温度之上。
将聚合物挤出成特定的形状,大多数情况下是圆筒形,是聚合物生产最后的加工步骤之一。挤出后,在形成可出售产品之前将产物冷却、切粒和,如果需要,再冷却一次。
对这种终端产品的要求之一是,它应该不含有空洞,也即是小气泡,因为这些空洞对随后的加工有负面的影响。此外,含有空洞的透明聚合物颗粒实际上很少有商业吸引力。
WO96/26241公开了一种生产聚合物颗粒的方法,其中,在44-95℃温度的水浴中挤出的聚合物带被冷却和切粒。得到的颗粒含有少于10%(体积)的空洞。但是这个数值仍然是不令人满意的。
现已发现一种方法,通过这种方法可以得到无空洞的颗粒,也即是空洞含量<1%(体积),优选甚至<0.1%(体积)的颗粒。
本发明提供了生产无空洞的聚合物颗粒的方法,其中,挤出后的聚合物以<50℃/秒的冷却速度,优选<20℃,冷却到聚合物的玻璃化转变温度Tg之上1-20℃,优选5-10℃,然后切粒。在本发明一个优选的实施方案中,在切粒过程中,粒料被冷却到≤100℃,优选≤90℃的温度。这可以通过例如,喷洒温度≤30℃的水来实现。
聚合物和冷却介质之间的温度差优选小于370℃。在一个优选的实施方案中,聚合物是采用温度40-80℃,优选50-60℃的水来冷却。特别优选地,挤出后的聚合物通过一个温度40-80℃,优选50-60℃的水浴。聚合物在水浴中的停留时间优选为3-10秒。在另一个实施方案中,挤出后的聚合物带是用温度40-80℃,优选50-60℃的水喷洒。
本发明方法适合于生产任何类无空洞的聚合物颗粒。但是,特别适合生产热塑性聚合物颗粒。本发明涉及的热塑性聚合物包括在有效的压力和温度下可变成可流动的所有塑料。可以给出的实例是聚苯乙烯、聚亚苯基、聚氨酯、聚酰胺、聚酯、聚丙烯酸酯、聚甲基丙烯酸酯、SAN和其共聚物。本发明的方法最适合生产无空洞的聚碳酸酯颗粒。
本发明涉及的聚碳酸酯既可以是均聚碳酸酯也可以是共聚碳酸酯。聚碳酸酯可以是线性的或已知方式支化的。在适合的聚碳酸酯中,直至80%(摩尔),优选从20%(摩尔)直至50%(摩尔),的碳酸酯基团可以被芳族二羧酸酯基团取代。这种聚碳酸酯,即碳酸的酸基和芳族二羧酸的酸基二者都进入分子链的聚碳酸酯,精确地说是芳族聚酯碳酸酯。它们包括在热塑性芳族聚碳酸酯的通称下。
关于聚碳酸酯生产的详细信息已经被罗列在过去约40年间的几百篇专利说明书中。作为例子,这里仅仅提及的参考文献是:Schnell,“聚碳酸酯的化学和物理”,Polymer Reviews,9卷,Interscience出版社,New York,London,Sydney 1964;D.C.PREVORSEK,B.T.DEBONAand Y.KESTEN,联合化学公司,合作研究中心,Morristown,NewJersey 07960,“聚(酯碳酸酯)共聚物的合成”,Journal of PolymerScience,Polymer Chemistry Edition,Vol.19,75-90(1980);D.Freitag,U.Grigo,P.R.Müller,N.Nouvertne’,BAYER公司,“聚碳酸酯”,聚合物科学和工程大全,11卷,第二版,1988,648-718页;Dres.U.Grigo,K.Kircher and P.R.Müller,“聚碳酸酯”,Becker/Braun,Kunststoff-Handbuch,3/1卷,聚碳酸酯、聚缩醛、聚酯、纤维素酯,Carl-Hanser Verlag,Munich,Vienna,1992,117-299页。
优选的热塑性聚碳酸酯的平均分子量Mv(通过在25℃CH2Cl2中测定的相对粘度确定,溶液浓度为0.5g/100ml CH2Cl2)为12,000-400,000,优选18,000-80,000,特别是22,000-60,000。
实施例
实施例1
制备好的聚碳酸酯挤出成型为直径约3mm的椭圆截面的圆柱形的带。挤出后,聚碳酸酯的温度为350℃。挤出带在水温恒定为60℃的水浴中冷却。挤出带在水浴中的停留时间为4秒钟。挤出带从水浴中取出时的温度为150℃。将挤出带切粒/造粒,并且在切粒过程中用水(T=25℃)喷洒,使其温度冷却到95℃。
这样制得的聚碳酸酯,通过计算1公斤粒料样品中含空洞的颗粒数确定空洞含量。结果粒料未发现有空洞。
实施例2
制备好的聚碳酸酯挤出成型为直径约3mm的椭圆截面的圆柱形的带。挤出后,聚碳酸酯的温度为350℃。挤出带在水温恒定为60℃的水浴中冷却。挤出带在水浴中的停留时间为4秒钟。挤出带从水浴中取出时的温度为150℃。在未进一步冷却的条件下将挤出带切粒。
得到的粒料含0.8%(体积)的空洞。
实施例3(比较例)
制备好的聚碳酸酯挤出成型为直径约3mm的椭圆截面的圆柱形的带。挤出后,聚碳酸酯的温度为400℃。挤出带在水温恒定为20℃的水浴中冷却。挤出带在水浴中的停留时间为4秒钟。挤出带从水浴中取出时的温度为95℃。在未进一步冷却的条件下将挤出带切粒。
这样得到的聚碳酸酯粒料含5%(体积)的空洞。
Claims (3)
1.一种生产无空洞的聚合物颗粒的方法,其中,在将聚合物挤出后,将聚合物以<50℃/秒的冷却速度冷却到聚合物的玻璃化转变温度Tg之上1-20℃,然后切粒。
2.权利要求1的方法,其中在切粒过程中,所述聚合物被冷却到≤100℃的温度。
3.权利要求1或2的方法,其中所述聚合物是聚碳酸酯。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19815717A DE19815717C2 (de) | 1998-04-08 | 1998-04-08 | Vakuolenfreie Polymergranulate |
DE19815717.7 | 1998-04-08 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN1296506A CN1296506A (zh) | 2001-05-23 |
CN1208374C true CN1208374C (zh) | 2005-06-29 |
Family
ID=7863969
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CNB998047953A Expired - Fee Related CN1208374C (zh) | 1998-04-08 | 1999-03-26 | 无空洞的聚合物颗粒 |
Country Status (11)
Country | Link |
---|---|
US (1) | US6551538B1 (zh) |
EP (1) | EP1090062B1 (zh) |
JP (1) | JP4231624B2 (zh) |
KR (1) | KR20010042522A (zh) |
CN (1) | CN1208374C (zh) |
AU (1) | AU3332499A (zh) |
BR (1) | BR9909443A (zh) |
DE (2) | DE19815717C2 (zh) |
ES (1) | ES2193692T3 (zh) |
RU (1) | RU2230661C2 (zh) |
WO (1) | WO1999052967A1 (zh) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE10310829A1 (de) * | 2003-03-13 | 2004-09-23 | Basf Ag | Thermoplastgranulate |
US20120205833A1 (en) * | 2011-02-11 | 2012-08-16 | Fina Technology, Inc. | Pelletizing high melt flow polystyrene |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3421647A1 (de) * | 1984-06-09 | 1985-12-12 | Bayer Ag, 5090 Leverkusen | Verfahren zur herstellung von polycarbonat-spritzgussformkoerpern |
US4581443A (en) * | 1984-10-09 | 1986-04-08 | Celanese Corporation | Production of improved pellets from melt-processable polymer which is capable of forming and anisotropic melt |
US5187256A (en) * | 1990-12-03 | 1993-02-16 | The Dow Chemical Company | Uniform distribution polycarbonate pellet |
WO1996026241A2 (en) * | 1995-02-14 | 1996-08-29 | The Dow Chemical Company | Polymer pellets, process for their preparation and moulded articles obtained therefrom |
US5846607A (en) * | 1997-06-30 | 1998-12-08 | Basf Corporation | Process for producing customized thermoplastic resins |
-
1998
- 1998-04-08 DE DE19815717A patent/DE19815717C2/de not_active Expired - Fee Related
-
1999
- 1999-03-26 JP JP2000543522A patent/JP4231624B2/ja not_active Expired - Fee Related
- 1999-03-26 WO PCT/EP1999/002088 patent/WO1999052967A1/de not_active Application Discontinuation
- 1999-03-26 AU AU33324/99A patent/AU3332499A/en not_active Abandoned
- 1999-03-26 CN CNB998047953A patent/CN1208374C/zh not_active Expired - Fee Related
- 1999-03-26 BR BR9909443-6A patent/BR9909443A/pt not_active IP Right Cessation
- 1999-03-26 US US09/647,227 patent/US6551538B1/en not_active Expired - Fee Related
- 1999-03-26 EP EP99914549A patent/EP1090062B1/de not_active Expired - Lifetime
- 1999-03-26 ES ES99914549T patent/ES2193692T3/es not_active Expired - Lifetime
- 1999-03-26 DE DE59904545T patent/DE59904545D1/de not_active Expired - Lifetime
- 1999-03-26 RU RU2000128022/12A patent/RU2230661C2/ru not_active IP Right Cessation
- 1999-03-26 KR KR1020007011160A patent/KR20010042522A/ko not_active Application Discontinuation
Also Published As
Publication number | Publication date |
---|---|
AU3332499A (en) | 1999-11-01 |
WO1999052967A1 (de) | 1999-10-21 |
DE59904545D1 (de) | 2003-04-17 |
BR9909443A (pt) | 2000-12-12 |
EP1090062B1 (de) | 2003-03-12 |
US6551538B1 (en) | 2003-04-22 |
JP4231624B2 (ja) | 2009-03-04 |
DE19815717C2 (de) | 2000-07-27 |
JP2002511353A (ja) | 2002-04-16 |
DE19815717A1 (de) | 1999-10-14 |
CN1296506A (zh) | 2001-05-23 |
ES2193692T3 (es) | 2003-11-01 |
RU2230661C2 (ru) | 2004-06-20 |
KR20010042522A (ko) | 2001-05-25 |
EP1090062A1 (de) | 2001-04-11 |
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