CN1154974A - Raw-silastic continuously polymerizing apparatus and technology thereof - Google Patents
Raw-silastic continuously polymerizing apparatus and technology thereof Download PDFInfo
- Publication number
- CN1154974A CN1154974A CN 96117710 CN96117710A CN1154974A CN 1154974 A CN1154974 A CN 1154974A CN 96117710 CN96117710 CN 96117710 CN 96117710 A CN96117710 A CN 96117710A CN 1154974 A CN1154974 A CN 1154974A
- Authority
- CN
- China
- Prior art keywords
- polymerization
- polymerization reactor
- preheater
- raw
- technology
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Silicon Polymers (AREA)
Abstract
The equipment for continuously polymerizing silastic raw rubber comprises preheater and polymerization reactor which are series-connected, and its polymerization reactor is formed of two or more than two SV type static mixers with one by one enlarged diameter and heating function which are series-connected. Its polymerization process includes: proportioning all materials; preheating in preheater and making polymerization in the polymerization reactor for above 0.5 hr to can obtain polymeric silastic raw rubber. Said invention features large production capacity, low power consumption, simple equipment and less investment.
Description
The invention belongs to the poly-unit and the technology of the poly-unit and the technology, particularly organopolysiloxane of macromolecular material.
The production of high molecular raw-silastic continuously is that the fifties end is industrialized.Usually adopt octamethylcyclotetrasiloxane (D in the production
4) or dimethyl siloxane ring body (DMC) under catalysis, reset polymerization, catalyzer is lost activity, remove volatile low-molecular weight compound again, promptly get rubber.The polymerization flow process has interrupter method and continuous processing two big classes, once adopts the polymerization reactor of various ways.
The polymerization of silicon rubber is a homogeneous reaction, and heat effect is less.The silicon rubber polymerization unit mainly solves is the material uniform problem of conducting heat.That is to say, when polyreaction begins, need material is heated to polymerization temperature (100～130 ℃) from normal temperature, under polymerization temperature, keep certain residence time then, to reach polymerization equilibrium.But, because the viscosity of polymerisate (being raw-silastic continuously) is quite high, about 1 * 10
4Pas makes that the heat transfer process in polymerization later stage is very difficult.For guaranteeing that whole materials all reach polymerization equilibrium, can only prolong the residence time of material in polymerization reactor.
The continuous processing polymerization unit that U.S. Dow Corning company adopts is a ribbon mixer, and U.S. Stanford institute has then used double-screw reactor.Though these equipment can solve the even problem of heat transfer of high-viscosity material preferably, the equipment price costliness is invested very greatly, and power consumption is also high.U.S. Pat 4,250,290 have adopted the unitary tubular reactor of static mixing with excellent forced convection characteristic as polymerization reactor and neutralization reactor, being used for production viscosity is that 0.5～500Pas (closes 500～500,000cp) the hydroxy-end capped polydimethylsiloxane of silicon of (25 ℃ of surveys), it is said can production viscosity be 0.01～1 also, 000Pas (10～1 * 10
6Cp) the end capped polydimethylsiloxane of three organopolysiloxanes of (25 ℃ of surveys), but do not provide the embodiment of any production high viscosity polysiloxane.Because the polymerization reactor that this patent is used is the static mixer of single diameter,, wants to prepare exit viscosity and reach 1 * 10 at the only several mPas of the material viscosity of ingress
6The product of mPas, this just means that the material that the front and back viscosity differences will be reached several ten thousand times remains plug flow under same speed, also will take into account flow velocity and resistance drop, this is practically impossible.This patent that Here it is will add chain terminator at the beginning to avoid the too high reason of polymer viscosity.In addition, viscosity is 1 * 10
6The polysiloxane of mPas, its molecular weight is less than 200,000, and as if the rubber as mixed milling type silicon rubber, prepared silicone rubber mechanical performance is very poor, does not have practical value.The used polymerizing catalyst of this patent also need add the neutralizing agent eliminate activity after polyreaction finishes, need set up neutralizing agent mixing tank and neutralization reactor and auxiliary facility, has increased facility investment and loss, has increased power consumption.And viscosity is up to 1 * 10
6The above material of mPas will mix with a small amount of neutralizing agent, thoroughly finishes neutralization reaction, also is very difficult.
The object of the present invention is to provide one the cover throughput big, raw material per pass conversion height, the monomer consumption rate is low, equipment is simple, invest little, the device and the technology of the continuous production high molecular raw-silastic continuously that power consumption is low.
The object of the present invention is achieved like this: preheater, polymerization reactor are together in series as poly-unit, and polymerization reactor wherein is in series by the heatable static mixer that the diameter more than 2 or 2 increases one by one.Continuous polymerization technique is: press D
4Or and DMC: end group is Me
3SiO or Me
2The dimethyl silicone oil of ViSiO: ethylene methacrylic radical siloxane ring body (VMC): elevated temperature heat is decomposed temporary catalyzer=100: 3 * 10
-2～3: 0～4: 1 * 10
-3～2 * 10
-2Ratio with each mixing of materials, dewater and send into preheater continuously to water content＜100ppm and be heated to 60～90 ℃, enter polymerization reactor then, be heated to 100～130 ℃, and make material in polymerization reactor, stop more than 0.5 hour, when treating that polymkeric substance reaches required viscosity or molecular weight, finish polyreaction.Wherein the dimethyl-silicon oil viscosity can be 1～1 * 10
5Mm
2Change in/s the scope.
After polymkeric substance is delivered to that taking off further heats up in the low molecule device and destroyed catalyzer and remove the lower molecular weight volatile matter, promptly get raw-silastic continuously.
Preheater can adopt tubular heater exchhanger or heatable static mixer.The used static mixer of polymerization reactor is a SV type static mixer, and diameter is 100～500mm, has chuck.SV type static mixer can be strengthened the forced convection heat transfer process of viscous liquid.Because its wavy channel has caused radical flow of material, because of the face heat transfer coefficient can improve several times.In the SV type static mixer, the heat transfer coefficient of viscous fluid just becomes to become with Reynolds number.The static mixer that is increased one by one by the diameter more than 2 or 2 is connected into the static mixer group, can adapt to the situation that material constantly increases in the heat transfer process medium viscosity well, can keep big as far as possible heat transfer coefficient, the material that can guarantee different viscosity again keeps the state of plug flow basically in each section reactor, the pressure of each section is fallen all to can be controlled in the reasonable range, be unlikely and cause too high pressure to fall, thereby the material in the whole polyreaction is heated evenly, assurance is produced viscosity greater than 1, and 000Pas (1 * 10
6Cp) (25 ℃ of surveys), molecular weight is greater than 400,000 raw-silastic continuously.
To decompose temporary catalyzer be silica alkanol ammonium salt to used elevated temperature heat in the polymerization technique, can be by Tetramethylammonium hydroxide and D
4Or DMC reacting by heating and preparing.
Fig. 1 is a poly-unit synoptic diagram of the present invention.
As shown in Figure 1, the raw material mixed liquor [1] that has dewatered (comprises D4Or DMC, dimethyl-silicon Oil, VMC, catalyst) drive through measuring pump [2], send into continuously preheater [3], chuck [7] In pass into heating or cooling medium [14], control temperature of charge be 60～90 ℃. Thing after the preheating Material enters the polymerization that the static mixer [4], [5], [6] that are increased one by one by three diameters are in series Reactor passes into steam [9], [11], [13] in chuck [8], [10], [12], make heating material To 100～130 ℃ polymerization temperature, and in polymer reactor, stop more than 0.5 hour. The material that polymerization is good [15] is sent to and is taken off low molecule device, is destroying catalyst and is removing the low molecular weight volatile thing After, namely get raw-silastic continuously.
Polyplant of the present invention and explained hereafter ability are big, can reach 300～1,000 ton/year. The mixed material inlet amount reaches 50～170kg/h. Primary raw material D4Or the conversion per pass of DMC Can be up to theoretical value (87.5%). D4Or the consumption rate of DMC is low, can be less than the 1010kg/ ton Glue. Polymerizing reactor equipment is simple, transmission mechanism-free, and power saving, the investment-saving is installed, is tieed up Protect simply polymer molecular weight height, excellent performance.
Embodiment one
Poly-unit is made up of preheater [3] and two static mixers [4], [5].Wherein preheater [3] is the coil pipe type heat exchanger of φ 32 * 3, and heat transfer area is 0.5 meter
2The barrel diameter of static mixer [4] is 150mm, long 900mm, interior dress diameter 150mm, the SV type static mixing unit of high 150mm.Chuck diameter 250mm, long 800mm.The barrel diameter of static mixer [5] is 300mm, long 900mm, interior dress diameter 300mm, the SV type static mixing unit of high 300mm.Chuck diameter 400mm, long 800mm.Mixing raw material consists of: DMC (or D
4) 100kg, dimethyl silicone oil (15～16mPas) 300g, VMC175g, Tetramethylammonium hydroxide 5g.
The mixing raw material input speed is 48kg/h, and preheater chuck [7] temperature is 70～80 ℃, and the vapor pressure of the chuck [8] of static mixer [4] is 0.3Mpa, and the vapor pressure of the chuck [10] of static mixer [5] is 0.5Mpa.With the mixing raw material (1) that dewatered through volume pump [2] warp let-off preheater successively [3], static mixer [4] and [5].The residence time of material in two static mixers [4], [5] is 1.5 hours, and gained rubber molecular weight is 660,000, and per pass conversion is 87.5%.Embodiment two
Poly-unit is made up of preheater [3] and 2 polymerization reactors [4], [5].Preheater [3] is a static mixer.Its barrel diameter is 150mm, long 900mm, the SV type static mixing unit of the high 150mm of interior dress diameter 150mm, chuck diameter 250mm, long 800mm.Polymerization reactor [4] is a static mixer.Its barrel diameter is 250mm, and long is 1000mm, interior dress diameter 250mm, the SV type static mixing unit of high 250mm.Chuck diameter 350mm, long 900mm.Polymerization reactor [5] is a static mixer.Its barrel diameter is 350mm, and long is 1050mm, interior dress diameter 350mm, the SV type static mixing unit of high 350mm.Chuck diameter 450mm, long 950mm.
Mixing raw material consists of: DMC (or D
4) 100kg, dimethyl silicone oil (5～6mmPas) 180g, VMC175g, Tetramethylammonium hydroxide 8g.
The mixing raw material input speed is 80kg/h, and pre-thermal jacket [7] temperature is 80～90 ℃, and the vapor pressure of the chuck [8] of static mixer [4] is 0.3Mpa, and the vapor pressure of the chuck [10] of static mixer [5] is 0.4～0.5Mpa.With the mixing raw material (1) that dewatered through volume pump [2] warp let-off preheater successively [3], static mixer [4], [5].The residence time of material in [4], [5] is 1.5 hours.Gained rubber molecular weight is 600,000.The DMC per pass conversion is 87.5%.Embodiment three
Poly-unit is made up of preheater [3] and three static mixer polymerization reactors [4], [5], [6].Wherein preheater [3] is the coil pipe type heat exchanger of φ 32 * 3,1 meter of heat transfer area
2The barrel diameter of static mixer [4] is 200mm, long 1000mm, interior dress diameter 200mm, the SV type static mixing unit of high 200mm.Chuck diameter 300mm, long 900mm.The barrel diameter of static mixer [5] is 300mm, long 900mm, interior dress diameter 300mm, the SV type static mixing unit of high 300mm.Chuck diameter 400mm, long 800mm.The barrel diameter of static mixer [6] is 400mm, long 1200mm, interior dress diameter 400mm, the SV type static mixing unit of high 400mm, chuck diameter 500mm, long 1100mm.
Mixing raw material consists of: DMC (or D
4) 100kg, dimethyl silicone oil (6～7mPas) 260g, VMC175g, Tetramethylammonium hydroxide 6g.
Mixing raw material input speed 166kg/h, preheater chuck [7] temperature is 80～90 ℃, chuck [8] vapor pressure of static mixer [4] is 0.1～0.2Mpa, chuck [10] vapor pressure of static mixer [5] is 0.3～0.4Mpa, and chuck [12] vapor pressure of static mixer [6] is 0.5～0.55Mpa.With the mixture (1) that dewatered through volume pump [2] warp let-off preheater successively [3], static mixer [4], [5], [6].The residence time of material in the polymerization reactor that three static mixers [4], [5], [6] are formed is 1.4 hours.Gained rubber molecular weight is 540,000, and the DMC per pass conversion is 87.5%.
Claims (3)
1. raw-silastic continuously continuous polymerization unit and technology, be that preheater, polymerization reactor are together in series as poly-unit, it is characterized in that polymerization reactor is to be in series by the heatable SV type static mixer that the diameter more than two or two increases one by one.
2. raw-silastic continuously continuous polymerization unit according to claim 1 and technology is characterized in that its polymerization technique is as follows: press D
4Or/and DMC: end group is Me
3SiO or Me
2The dimethyl silicone oil of ViSiO: ethylene methacrylic radical siloxane ring body: elevated temperature heat is decomposed temporary catalyzer=100: 3 * 10
-2～3: 0～4: 1 * 10
-3～2 * 10
-2Ratio with each mixing of materials, dewater to water content less than 100ppm after, send into preheater continuously and be heated to 60～90 ℃, enter polymerization reactor then, be heated to 100～130 ℃, and make material in polymerization reactor, stop more than 0.5 hour, when treating that polymkeric substance reaches required viscosity or molecular weight, finish polyreaction.
3. according to described raw-silastic continuously continuous polymerization unit of claim 1.2 and technology, it is characterized in that it is silica alkanol ammonium salt that elevated temperature heat is decomposed temporary catalyzer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96117710A CN1113923C (en) | 1996-09-12 | 1996-09-12 | Raw-silastic continuously polymerizing apparatus and technology thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96117710A CN1113923C (en) | 1996-09-12 | 1996-09-12 | Raw-silastic continuously polymerizing apparatus and technology thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1154974A true CN1154974A (en) | 1997-07-23 |
| CN1113923C CN1113923C (en) | 2003-07-09 |
Family
ID=5124534
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96117710A Expired - Lifetime CN1113923C (en) | 1996-09-12 | 1996-09-12 | Raw-silastic continuously polymerizing apparatus and technology thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1113923C (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100444947C (en) * | 2005-06-16 | 2008-12-24 | 中国纺织科学研究院 | Lactide analog monomer continuous polymerization device and process |
| CN102199355A (en) * | 2011-04-23 | 2011-09-28 | 茂名市信翼化工有限公司 | Preparation method for room temperature vulcanized silicon rubber |
| CN102924721A (en) * | 2012-11-22 | 2013-02-13 | 深圳市森日有机硅材料有限公司 | Method for continuously preparing vinyl silicone oil |
| CN102977371A (en) * | 2012-11-19 | 2013-03-20 | 福建省邵武市永晶化工有限公司 | Fluorosilicone rubber continuous-polymerization method |
| CN103073722A (en) * | 2012-12-19 | 2013-05-01 | 宜昌科林硅材料有限公司 | Continuous preparation technology of high-purity low-viscosity dimethicone |
| CN103554499A (en) * | 2013-09-29 | 2014-02-05 | 安徽同丰橡塑工业有限公司 | Production technology for heat-vulcanized silicone rubber raw rubber |
| CN104072773A (en) * | 2013-06-27 | 2014-10-01 | 上海威宁整形制品有限公司 | Device and method for preparing ultrahigh-viscosity ultrahigh-elasticity breast implant filler |
| CN110394143A (en) * | 2019-08-21 | 2019-11-01 | 兖州煤业股份有限公司 | A kind of coal resolution tubular type reaction unit |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5043694A (en) * | 1973-08-28 | 1975-04-19 | ||
| DE2705556C3 (en) * | 1977-02-10 | 1980-07-31 | Bayer Ag, 5090 Leverkusen | Polymerization reactor |
| AU5900880A (en) * | 1979-06-18 | 1981-01-08 | General Electric Company | Continuous manufacture of siloxane polymers |
-
1996
- 1996-09-12 CN CN96117710A patent/CN1113923C/en not_active Expired - Lifetime
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100444947C (en) * | 2005-06-16 | 2008-12-24 | 中国纺织科学研究院 | Lactide analog monomer continuous polymerization device and process |
| CN102199355A (en) * | 2011-04-23 | 2011-09-28 | 茂名市信翼化工有限公司 | Preparation method for room temperature vulcanized silicon rubber |
| CN102199355B (en) * | 2011-04-23 | 2012-09-19 | 广东信翼新材料股份有限公司 | Preparation method for room temperature vulcanized silicon rubber |
| CN102977371B (en) * | 2012-11-19 | 2014-12-17 | 福建省邵武市永晶化工有限公司 | Fluorosilicone rubber continuous-polymerization method |
| CN102977371A (en) * | 2012-11-19 | 2013-03-20 | 福建省邵武市永晶化工有限公司 | Fluorosilicone rubber continuous-polymerization method |
| CN102924721A (en) * | 2012-11-22 | 2013-02-13 | 深圳市森日有机硅材料有限公司 | Method for continuously preparing vinyl silicone oil |
| CN102924721B (en) * | 2012-11-22 | 2013-12-25 | 深圳市森日有机硅材料有限公司 | Method for continuously preparing vinyl silicone oil |
| CN103073722A (en) * | 2012-12-19 | 2013-05-01 | 宜昌科林硅材料有限公司 | Continuous preparation technology of high-purity low-viscosity dimethicone |
| CN104072773A (en) * | 2013-06-27 | 2014-10-01 | 上海威宁整形制品有限公司 | Device and method for preparing ultrahigh-viscosity ultrahigh-elasticity breast implant filler |
| CN104072773B (en) * | 2013-06-27 | 2016-06-29 | 上海威宁整形制品有限公司 | A kind of hyperviscosity, the preparation facilities of super-elastic breast prosthesis filler and preparation method |
| CN103554499A (en) * | 2013-09-29 | 2014-02-05 | 安徽同丰橡塑工业有限公司 | Production technology for heat-vulcanized silicone rubber raw rubber |
| CN110394143A (en) * | 2019-08-21 | 2019-11-01 | 兖州煤业股份有限公司 | A kind of coal resolution tubular type reaction unit |
| CN110394143B (en) * | 2019-08-21 | 2024-06-07 | 兖矿能源集团股份有限公司 | Tubular reaction device is cleared up to coal |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1113923C (en) | 2003-07-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4250290A (en) | Process for the continuous manufacture of siloxane polymers | |
| CN101031592B (en) | Method for the continuous implementation of polymerisation processes | |
| US6555629B1 (en) | Method and device for continuous production of polymers | |
| RU98119840A (en) | POLYMERIZATION OF OLEFINS FROM SOLUTION | |
| EP1768775A1 (en) | Method and device for the gradual production of polymers using melt condensation | |
| CN1154974A (en) | Raw-silastic continuously polymerizing apparatus and technology thereof | |
| JPS60202124A (en) | Silicone rubber continuous manufacture | |
| US5319120A (en) | Polymerization reactor and polymerization process | |
| CN107090606A (en) | A kind of method for producing multifunctional different polyester fiber | |
| CH637309A5 (en) | CONTINUOUS PROCEDURE FOR CARRYING OUT REACTIONS REGARDING FABRIC TRANSPORT. | |
| US4849182A (en) | Apparatus and method for the continuous production of aqueous polymer solutions | |
| US3679651A (en) | Method of polymerizing styrene | |
| WO2024051671A1 (en) | Polymerization-termination device and method for continuous production of organopolysiloxanes | |
| JPH0113726B2 (en) | ||
| JPS61190503A (en) | Production of polymethyl methacrylate | |
| CN1242825C (en) | Polymer solution preheater and method for preheating such solutions | |
| EP2281009A1 (en) | Process and apparatus for preparing biopolymers | |
| US7300999B2 (en) | Method of making polyesters | |
| CN113429557B (en) | Continuous preparation method of low-viscosity polyether polyol | |
| CN101888899B (en) | Process for preparing low impurity polyester | |
| JP3323211B2 (en) | Continuous production method of siloxane polymer | |
| CN111298752A (en) | Continuous production equipment for free radical polymerization and use method thereof | |
| EP1302501B1 (en) | Process and equipment for post-polycondensation in the molten state of plastic materials | |
| IE42018B1 (en) | Process for the continuous polymerisation of lactams | |
| US4965298A (en) | Preparation and cooling of aqueous polymer solution |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ASS | Succession or assignment of patent right |
Owner name: SOUTHWEST HUAJI CO., LTD. Free format text: FORMER OWNER: CHENGUANG CHEMICAL RESEARCH ACADEMY (CHENGDU), MINISTRY OF CHEMICAL INDUSTRY Effective date: 20040716 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20040716 Address after: 618400, Sichuan, Shifang two river town Patentee after: Southwest Chemical Limited by Share Ltd Address before: 610041 No. four, South Renmin Road, Sichuan, Chengdu province 30 Patentee before: Chenguang Chemical Research Academy (chengdu), Ministry of Chemical Industry |
|
| PP01 | Preservation of patent right |
Effective date of registration: 20051024 Pledge (preservation): Preservation |
|
| PD01 | Discharge of preservation of patent |
Date of registration: 20060424 Pledge (preservation): Preservation |
|
| CX01 | Expiry of patent term |
Granted publication date: 20030709 |
|
| EXPY | Termination of patent right or utility model |