CN106947072A - A kind of preparation technology of makrolon - Google Patents
A kind of preparation technology of makrolon Download PDFInfo
- Publication number
- CN106947072A CN106947072A CN201710263179.3A CN201710263179A CN106947072A CN 106947072 A CN106947072 A CN 106947072A CN 201710263179 A CN201710263179 A CN 201710263179A CN 106947072 A CN106947072 A CN 106947072A
- Authority
- CN
- China
- Prior art keywords
- makrolon
- polycondensation
- preparation technology
- added
- reactor
- 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.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/20—General preparatory processes
- C08G64/30—General preparatory processes using carbonates
- C08G64/307—General preparatory processes using carbonates and phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
A kind of preparation technology of makrolon, comprises the following steps：S1, generalWithMelted, be added in transesterification reactor respectively, and add catalyst and carry out ester exchange reaction, obtain oligomer；S2, the resulting oligomer in S1 is added in polycondensation reactor carries out polycondensation reaction, obtain polycondensation product；S3, the polycondensation product in S2 is added in extruder be extruded, cool down and dry by water-bath after extrusion, be transported in comminutor and carry out shear granulation, the polycarbonate pellets of finished product；Wherein R is cycloalkyl, and R ' and R " are alkyl or phenyl.By using above-mentioned technical proposal, the makrolon of bisphenol Z series is prepared using the mode of melting, the use of a large amount of solvents is so saved, so as to not only improve saving resource, is not easy to cause environment excessive pollution again.
Description
Technical field
The present invention relates to chemical production field, more particularly to a kind of preparation technology of makrolon.
Background technology
Makrolon (abbreviation PC) is the high molecular polymer containing carbonate group in strand, due to the spy in its structure
Different property, as the most fast general engineering plastic of growth rate in five large-engineering plastics.Meanwhile, it can be divided according to the structure of ester group
For polytypes such as aliphatic, aromatic series, aliphatic-aromatics.Wherein due to aliphatic and aliphatic-aromatic makrolon
Mechanical performance it is relatively low, so as to limit its application in terms of engineering plastics.Only aromatic copolycarbonate is obtained at present
Industrialized production.The especially makrolon of bisphenol A-type, it has preferable mechanical strength, excellent heat resistance and resistance to punching
The advantages of hit intensity is high, and its preparation technology is also more ripe, so being applied to various fields.
For example applied in organic photoconductor, but because it is dissolved only in alkyl halide, can be in film during film in use
The middle a small amount of alkyl halide of residual, can make transmission material when optical conductor is used due to alkyl halide generation photochemical effect generation chlorine radical
Material dissociation, accelerates the aging of optical conductor, shortens the service life of optical conductor.And bisphenol Z type polycarbonate has general bisphenol A-type
The advantage of makrolon, and it can be dissolved in aromatic hydrocarbons, can be prevented effectively from the disadvantages mentioned above of bisphenol A polycarbonate, so that
Rest potential and dark-decay rate can be effectively reduced, optical conductor application performance is improved.
And as long as prior art bisphenol Z type polycarbonate is used as what raw material was produced with triphosgene and bisphenol Z, example
Such as the Chinese patent of Application No. 200610130498《A kind of synthetic method of bisphenol Z type polycarbonate》Disclose a kind of bis-phenol
The synthetic method of Z-type makrolon, bisphenol Z is dissolved in the sodium hydrate aqueous solution that mass concentration is 3% by it, -10~10
It is 0.33~0.67 triphosgene alkyl halide solution to be added at DEG C with bisphenol Z mol ratio, and it is 5% to add with bisphenol Z mol ratio
After~15% TBAB and triethylamine, liquid-liquid two-phase polycondensation is carried out 2~3 hours in 20~40 DEG C.Reaction terminates
Afterwards, deionized water cyclic washing is directly used, until not chloride ion-containing in aqueous phase, adds methanol stirring, precipitation is isolated and obtains double
Phenol Z-type makrolon.Although the raw material of the synthetic method is easy to get, and reaction temperature is low, and good product quality, heat endurance is good, is easy to
Realize industrialized production.Obtained product viscosity average molecular weigh scope is 3 × 104~14 × 104, product yield is reachable in terms of bisphenol Z
90%.But, it is necessary to which substantial amounts of alkali and alkyl halide, which are used as, solvent, in such production process during whole prepare
Also the substantial amounts of wasting of resources and environmental pollution are easily caused.
The content of the invention
It is an object of the invention to provide a kind of preparation technology of makrolon, its can not only reduce resource waste and
The pollution of environment, and operating procedure is also simplified.
The present invention above-mentioned purpose technical scheme is that：A kind of preparation technology of makrolon,
Comprise the following steps：
S1, generalMelted, be added to respectively
In transesterification reactor, and catalyst progress ester exchange reaction is added, obtain oligomer；
S2, the resulting oligomer in S1 is added in polycondensation reactor carries out polycondensation reaction, obtain polycondensation product；
S3, the polycondensation product in S2 is added in extruder be extruded, cool down and dry by water-bath after extrusion, conveyed
Shear granulation, the polycarbonate pellets of finished product are carried out into comminutor；
Wherein R is cycloalkyl, and R ' and R " are alkyl or phenyl.
Preferably,For bisphenol Z,For carbonic acid
Diphenyl ester.
Preferably, the mol ratio of diphenyl carbonate and bisphenol Z is 1.03~1.05.
By using above-mentioned technical proposal, the makrolon of bisphenol Z series is prepared using the mode of melting, is so saved
The use of a large amount of solvents, so as to not only improve saving resource, is not easy to cause environment excessive pollution again.
It is resulting pre- so during ester exchange also, the amount that diphenyl carbonate is added is excessive with bisphenol Z compared with
Polymers molecule two ends are more strongly active ester group, so as to advantageously ensure that the activity of prepolymer molecule, so treat prepolymer
It is fed to after polycondensation reactor, it becomes possible to rapidly carry out polycondensation reaction, so as to substantially increase the production effect of makrolon
Rate.
Preferably, the catalyst is the mixture in halo lithium and lithium triethylborohydride.
Preferably, the halogenated aluminum lithium is lithium chloride.
By using above-mentioned technical proposal, boron triethyl lithium chloride has stronger selection compared to its parent tetrahydro boron lithium
Reproducibility, the ester group in diphenyl carbonate efficiently can be reduced into hydroxyl by it.And lithium chloride is used as a part for catalyst
The progress of new esterification can be improved.So that under the collective effect of lithium chloride and boron triethyl lithium chloride, can be significantly
Improve bisphenol Z and diphenyl carbonate carries out ester exchange reaction.
Preferably, when polycondensation reaction is carried out in S2, vavuum pump carries out vacuumize process, polycondensation reaction to polycondensation reactor
The pressure of device is in 0.1~0.01kPa, and temperature is 290~310 DEG C.
By using above-mentioned technical proposal, due to polycarbonate production during can produce substantial amounts of phenol, it can shadow
The yield of makrolon is rung, thus polycondensation reactor vacuum state so can rapidly be removed phenol by vavuum pump.
Preferably, polycondensation process in S2, defoamer is added into polycondensation reactor.
By using above-mentioned technical proposal, because the process that phenol comes out from volatility of raw material is mainly entered in the way of bubbling
Capable, and during polycondensation reaction, the viscosity of raw material has compare big, and bubble is difficult to rupture, so as to will influence
The final product quality of makrolon.Therefore, the addition of defoamer can rapidly eliminate the bubble in polycondensation process, from
And be conducive to easily improving the clearance of phenol.
Preferably, the defoamer is dimethyl silicone polymer.
By using above-mentioned technology, dimethyl silicone polymer not only has the effect of common defoamer, can rapidly make
Bubble ruptures.Meanwhile, a small amount of copolymer can also be formed with makrolon during polycondensation reaction, so poly-
Silica group is then introduced in carbonate molecule chain, so as to substantially increase the hardness and marresistance of makrolon.
Preferably, in S1 in ester-exchange reaction, the temperature of transesterification reactor is at 210~280 DEG C, and pressure is 10
~0.1kPa.
To obtain the makrolon of HMW, it is necessary to the uninterrupted and removal reaction life from reactant system as much as possible
Into low molecule phenol product or diphenyl carbonate.And transesterification reactor is in larger vacuum state in the operating condition,
So also it is easier to low molecule phenol product or diphenyl carbonate is evaporated from material system, afterwards then can be very square
Just it is pulled out.
Preferably, in S1 ester exchange reaction mid-term, into transesterification reactor add Halogen dissaving polymer.
By using above-mentioned technical proposal, the molecule of such makrolon will introduce Halogen dissaving polymer, pass through
Using Halogen dissaving polymer as polyacrylic flow ability modifying agent, do not changing the molecular weight and molecular weight point of acrylic resin
In the case of cloth, polyacrylic mobility can be improved, products appearance is improved, energy consumption is reduced, production cost is reduced.
In summary, the invention has the advantages that：
1st, bisphenol Z and diphenyl carbonate are subjected to ester exchange reaction in the molten state and makrolon is made in polycondensation reaction, saved
The input of solvent has been gone, resource has not only been saved but also the pollution to environment can be reduced；
2nd, using dissaving polymer is added in the polycondensation process of makrolon, so makrolon mechanical property is being ensured
Under the premise of, the mobile performance of makrolon can be improved again；
3rd, during polycondensation, defoamer is added into polycondensation reactor, can so accelerate the rupture of bubble, so that favorably
In vavuum pump by the small molecule phenol or diphenyl carbonate that are produced in course of reaction, so as to be conducive to obtaining the poly- carbon of HMW
Acid esters.
Brief description of the drawings
Fig. 1 is the preparation technology flow chart of makrolon；
Fig. 2 is the preparation flow figure of dissaving polymer.
Embodiment
Below in conjunction with accompanying drawing, 1 couple of present invention is described in further detail.
The present invention be withFor raw material,
Ester exchange reaction occurs in the state of melting, polycondensation reaction is then carried out again makrolon is made.Wherein R is cycloalkyl, example
Such as cyclopropyl, cyclobutyl, cyclopenta, ring the eleventh of the twelve Earthly Branches base, and R ' and R " is alkyl or phenyl, such as methyl, ethyl, propyl group and benzene
Base.Herein,Respectively bisphenol Z and carbonic acid
Diphenyl ester.
Embodiment one,
Step one：Diphenyl carbonate and bisphenol Z are put into using mol ratio as 1.03, respectively in two melting tanks and heated up
Full-fusing；
Step 2：The molten mass of diphenyl carbonate and bisphenol Z is delivered in same mixing batch can and is stirred mixing, stirring
Rotating speed is 800rpm, and the time of stirring is 10min；
Step 3：Mixture in blending tank is once delivered in the transesterification reactor with knockout tower and vavuum pump, and added
Enter catalyst and carry out ester exchange reaction, dissaving polymer is added during question response mid-term, reaction total duration is 1 hour, obtains pre-
Temperature in poly- reactant, wherein ester-exchange reaction is 210 DEG C, and pressure is 10kPa；
Step 4：Prepolymerization reaction thing is delivered in the polycondensation reactor with condenser and vavuum pump, and puts into defoamer, is carried out
Polycondensation reaction, reaction total duration is 2 hours, obtains semi-finished polycarbonate, the temperature of polycondensation reactor is 290 DEG C, and pressure exists
0.1kPa, the yield of makrolon is 95.2%, and weight average molecular weight Mw is 21000.
Step 5：Semi-finished polycarbonate is passed into extrusion and carries out further melting extrusion, the poly- carbonic acid of extrusion
Ester bar is carried out after water-bath cooling, is transported under drier and is carried out cold air drying, is transported in comminutor is cut again afterwards
Granulation is cut, the polycarbonate pellets of finished product are obtained.
Herein, catalyst is the mixture of halo lithium and lithium triethylborohydride, and halo lithium can be lithium chloride, bromine
Change lithium and lithium iodide, preferably lithium chloride, can so be reduced ester group by the strong selective reduction of lithium triethylborohydride
Into hydroxyl, then again in the presence of lithium chloride, new esterification is rapidly carried out, is handed over so as to also be considerably improved whole ester
Change the efficiency of reaction.Here lithium chloride and lithium triethylborohydride are mixed with mass ratio 1: 1, meanwhile, overall catalysis
Agent quality is the 3% of diphenyl carbonate quality.
Also, defoamer is organic silicon defoamer, preferably dimethyl silicone polymer defoamer, it, which not only has, typically disappears
The characteristic of infusion, can be quickly that the bubble in reactant ruptures, so as to be conducive to vavuum pump by the small molecule of generation
Phenol and diphenyl carbonate are got rid of, at the same also can the effect of being copolymerized with makrolon, silica group is incorporated into poly- carbon
In acid esters, the hardness and marresistance of makrolon are so also just improved.Here the quality of dimethyl silicone polymer is pre-polymerization
The 2% of reactant weight.
In addition, as shown in Figure 2, Halogen dissaving polymer is prepared from by following preparation method：First by reaction system
In air drain, be passed through inert gas, according to quantity first add BDO-two-(2- bromo acids) and butyl acetate
Reaction unit, then puts into reaction unit successively by iron chloride, α-methylstyrene, ascorbic acid and PCDI, is stirred at 70 DEG C
Reaction 17h is mixed, is used1H-NMR magnetic resonance detection double bond conversion rates, conversion ratio reaches that more than 80% is reaction end, then adds
Enter tert-dodecylmercaotan, 15h is reacted under the conditions of 35 DEG C, add benzoyl peroxide and remove excessive tertiary dodecyl sulphur
Alcohol, the Halogen dissaving polymer is obtained after precipitation.
Here obtained Halogen dissaving polymer has obtained the modification of tert-dodecylmercaotan, and it is in polycondensation reactor
There is splendid intermiscibility with prepolymerization reaction thing.Wherein according to the molar ratio, BDO-two-(2- bromo acids): chlorination
Iron=100: 0.03, ascorbic acid: iron chloride=15: 1, ascorbic acid: PCDI=1: 1, BDO-two-(2- bromos are different
Butyric acid): tert-dodecylmercaotan=1: 2, tert-dodecylmercaotan: benzoyl peroxide=1: 0.7.
Embodiment two to example IV and comparative example one and comparative example two in following table is with the operation of embodiment one
Step is foundation, and wherein comparative example one does not add dissaving polymer, and comparative example two is not added：
Moreover, according to the step of embodiment three and raw material be used for carry out comparative example one and comparative example two makrolon system
Standby, the difference of wherein comparative example one and embodiment three is not add Halogen dissaving polymer, and comparative example two and embodiment
Three difference is not add defoamer.
Method of testing：
The measure of plastic flow property：GB/T 21060-2007；
Plastic tensile performance test：GB1040-92；
Plastics-Oetermination of flexural properties method：GB/T 9341-2000；
Rockwell hardness：GB/T3398.2-2008；
Plastics scratch resistance method for testing performance：JBT 6072-1992.
According to prepared by above-mentioned detection method detection embodiment one to embodiment five and comparative example one and comparative example two
Makrolon properties, obtain following table result：
Makrolon can be drawn in the case where mechanical property does not have situation of change by being compared by embodiment three with comparative example one, mobility
It is greatly improved, so as to advantageously reduce production cost.And embodiment three is compared with comparative example two can draw the present invention
Makrolon hardness and marresistance can be obtained for huge lifting.Also, the preparation process letter of whole makrolon
It is single, and energy consumption reduction, so that production cost is greatly reduced, and efficiency is higher than the production method of similar makrolon, and
The makrolon produced is more suitably applied to prepare optical conductor.
This specific embodiment is only explanation of the invention, and it is not limitation of the present invention, people in the art
Member can make the modification without creative contribution to the present embodiment as needed after this specification is read, but as long as at this
All protected in the right of invention by Patent Law.
Claims (10)
1. a kind of preparation technology of makrolon, comprises the following steps：
S1, generalMelted, be added to respectively
In transesterification reactor, and catalyst progress ester exchange reaction is added, obtain oligomer；
S2, the resulting oligomer in S1 is added in polycondensation reactor carries out polycondensation reaction, obtain polycondensation product；
S3, the polycondensation product in S2 is added in extruder be extruded, cool down and dry by water-bath after extrusion, conveyed
Shear granulation, the polycarbonate pellets of finished product are carried out into comminutor；
Wherein R is cycloalkyl, and R ' and R " are alkyl or phenyl.
2. a kind of preparation technology of makrolon according to claim 1, it is characterised in that：For bisphenol Z,For diphenyl carbonate.
3. a kind of preparation technology of makrolon according to claim 2, it is characterised in that：Diphenyl carbonate and bisphenol Z
Mol ratio be 1.03~1.05.
4. a kind of preparation technology of makrolon according to claim 1, it is characterised in that：The catalyst is halo lithium
With the mixture in lithium triethylborohydride.
5. a kind of preparation technology of makrolon according to claim 4, it is characterised in that：The halo lithium is chlorination
Lithium.
6. a kind of preparation technology of makrolon according to claim 1, it is characterised in that：Polycondensation reaction is carried out in S2
When, vavuum pump carries out vacuumize process to polycondensation reactor, and the pressure of polycondensation reactor is in 0.1~0.01kPa, and temperature is 290
~310 DEG C.
7. a kind of preparation technology of makrolon according to claim 6, it is characterised in that：Polycondensation process in S2,
Defoamer is added into polycondensation reactor.
8. a kind of preparation technology of makrolon according to claim 7, it is characterised in that：The defoamer is poly- diformazan
Radical siloxane.
9. a kind of preparation technology of makrolon according to claim 1, it is characterised in that：Ester-exchange reaction in S1
In, the temperature of transesterification reactor is at 210~280 DEG C, and pressure is in 10~0.1kPa.
10. a kind of preparation technology of makrolon according to claim 1, it is characterised in that：Ester exchange reaction in S1
Mid-term, Halogen dissaving polymer is added into transesterification reactor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710263179.3A CN106947072A (en) | 2017-04-20 | 2017-04-20 | A kind of preparation technology of makrolon |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710263179.3A CN106947072A (en) | 2017-04-20 | 2017-04-20 | A kind of preparation technology of makrolon |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106947072A true CN106947072A (en) | 2017-07-14 |
Family
ID=59476322
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710263179.3A Pending CN106947072A (en) | 2017-04-20 | 2017-04-20 | A kind of preparation technology of makrolon |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106947072A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109265951A (en) * | 2018-08-03 | 2019-01-25 | 宁波浙铁大风化工有限公司 | The preparation process of polycarbonate |
| CN109265670A (en) * | 2018-08-03 | 2019-01-25 | 宁波浙铁大风化工有限公司 | A kind of preparation process of polycarbonate |
| WO2020173110A1 (en) * | 2019-02-25 | 2020-09-03 | 台州市欧威家具有限公司 | Method for preparing polycarbonate |
| CN113801313A (en) * | 2021-09-22 | 2021-12-17 | 宁波浙铁大风化工有限公司 | Preparation method of high molecular weight polycarbonate and polycarbonate |
| CN116178692A (en) * | 2023-02-21 | 2023-05-30 | 深圳市远景医疗器械模具有限公司 | Composite material for virus preservation tube and preparation method thereof |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0413190A2 (en) * | 1989-08-12 | 1991-02-20 | Bayer Ag | Polycarbonates prepared from n-alkyl substituted cyclohexylidene diphenols |
| CN1053246A (en) * | 1989-12-28 | 1991-07-24 | 日本Ge塑料株式会社 | The method for preparing aromatic polycarbonate |
| JPH05148354A (en) * | 1991-11-28 | 1993-06-15 | Daicel Chem Ind Ltd | Production of polycarbonate |
| CN1088946A (en) * | 1992-10-14 | 1994-07-06 | 大世吕化学工业株式会社 | The preparation method of polycarbonate |
| CN1500105A (en) * | 2001-01-12 | 2004-05-26 | ͨ�õ�����˾ | Melt polycarbonate catalyst systems |
| CN1701085A (en) * | 2002-10-07 | 2005-11-23 | 通用电气公司 | Method of polycarbonate preparation |
| CN1957017A (en) * | 2004-05-20 | 2007-05-02 | 出光兴产株式会社 | Polycarbonate resin and electrophotographic photoreceptor using the same |
| CN103562274A (en) * | 2011-05-17 | 2014-02-05 | 迈图高新材料有限责任公司 | Polysiloxane-polyorgano block copolymers |
| CN104804197A (en) * | 2015-04-16 | 2015-07-29 | 科达斯特恩(常州)汽车塑件系统有限公司 | Halogen-free hyperbranched polymer and modified polypropylene containing same |
| CN106279227A (en) * | 2016-07-15 | 2017-01-04 | 车荣睿 | The preparation method of lithium triethylborohydride tetrahydrofuran solution |
-
2017
- 2017-04-20 CN CN201710263179.3A patent/CN106947072A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0413190A2 (en) * | 1989-08-12 | 1991-02-20 | Bayer Ag | Polycarbonates prepared from n-alkyl substituted cyclohexylidene diphenols |
| CN1053246A (en) * | 1989-12-28 | 1991-07-24 | 日本Ge塑料株式会社 | The method for preparing aromatic polycarbonate |
| JPH05148354A (en) * | 1991-11-28 | 1993-06-15 | Daicel Chem Ind Ltd | Production of polycarbonate |
| CN1088946A (en) * | 1992-10-14 | 1994-07-06 | 大世吕化学工业株式会社 | The preparation method of polycarbonate |
| CN1500105A (en) * | 2001-01-12 | 2004-05-26 | ͨ�õ�����˾ | Melt polycarbonate catalyst systems |
| CN1701085A (en) * | 2002-10-07 | 2005-11-23 | 通用电气公司 | Method of polycarbonate preparation |
| CN1957017A (en) * | 2004-05-20 | 2007-05-02 | 出光兴产株式会社 | Polycarbonate resin and electrophotographic photoreceptor using the same |
| CN103562274A (en) * | 2011-05-17 | 2014-02-05 | 迈图高新材料有限责任公司 | Polysiloxane-polyorgano block copolymers |
| CN104804197A (en) * | 2015-04-16 | 2015-07-29 | 科达斯特恩(常州)汽车塑件系统有限公司 | Halogen-free hyperbranched polymer and modified polypropylene containing same |
| CN106279227A (en) * | 2016-07-15 | 2017-01-04 | 车荣睿 | The preparation method of lithium triethylborohydride tetrahydrofuran solution |
Non-Patent Citations (9)
| Title |
|---|
| 张巧玲: "《化学工艺学》", 31 July 2015, 国防工业出版社 * |
| 李华: "《主要包装物特性与资源再生实用手册》", 31 October 2010, 中国环境科学出版社 * |
| 李安平: "《食品添加剂原料与安全使用》", 30 September 2011, 国防科技大学出版社 * |
| 林华: "《石油化学工业技术与经济》", 31 December 1990, 第313页 * |
| 梁增田: "《塑料涂料与涂装》", 31 March 2006, 科学技术文献出版社 * |
| 甘绍宁: "《专利信息利用的实践》", 31 January 2016, 知识产权出版社 * |
| 谢如刚: "《现代有机化学》", 31 January 2007, 华东理工大学出版社 * |
| 韦军: "《高分子合成工艺学》", 28 February 2011, 华东理工大学出版社 * |
| 马洛平: "《消除有害泡沫技术》", 31 December 1987, 化学工业出版社 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109265951A (en) * | 2018-08-03 | 2019-01-25 | 宁波浙铁大风化工有限公司 | The preparation process of polycarbonate |
| CN109265670A (en) * | 2018-08-03 | 2019-01-25 | 宁波浙铁大风化工有限公司 | A kind of preparation process of polycarbonate |
| WO2020173110A1 (en) * | 2019-02-25 | 2020-09-03 | 台州市欧威家具有限公司 | Method for preparing polycarbonate |
| CN113801313A (en) * | 2021-09-22 | 2021-12-17 | 宁波浙铁大风化工有限公司 | Preparation method of high molecular weight polycarbonate and polycarbonate |
| CN116178692A (en) * | 2023-02-21 | 2023-05-30 | 深圳市远景医疗器械模具有限公司 | Composite material for virus preservation tube and preparation method thereof |
| CN116178692B (en) * | 2023-02-21 | 2024-10-18 | 深圳市远景医疗器械模具有限公司 | Composite material for virus preservation tube and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106947072A (en) | A kind of preparation technology of makrolon | |
| CN111378101A (en) | Preparation method of biodegradable carbon dioxide-based polyester-polycarbonate terpolymer | |
| CN103113533B (en) | Copolymer of poly lactic acid and preparation method thereof, polydactyl acid | |
| CN102516519B (en) | Method for preparing polycarbonate | |
| CN107474201A (en) | A kind of preparation method of high thermal stability end capped polyether ether ketone resin | |
| CN105801863B (en) | Preparation method of hydroxyl-terminated polymethylethylsiloxane | |
| CN115028823A (en) | Preparation method of copolycarbonate, copolycarbonate and application thereof | |
| WO2022183637A1 (en) | Chlorosulfonated poly(propylene carbonate), and preparation method therefor and use thereof | |
| CN103556289B (en) | Creep-resistant polyester and its preparation method | |
| CN102372848B (en) | A kind of method of preparing polycarbonate through melt transesterification technology | |
| CN115433442B (en) | Biodegradable tough composite material and preparation method thereof | |
| CN100386360C (en) | Copoaromatic ether and preparation thereof | |
| CN103788382B (en) | Star-structured polyethylene and preparation method thereof | |
| CN107250218A (en) | New polysiloxane and the Copolycarbonate prepared using it | |
| CN103541037B (en) | High-strength safety belt industrial yarn of a kind of creep resistant polyester and preparation method thereof | |
| CN103774273B (en) | Anti-core suction type industrial yarn of a kind of creep resistant polyester and preparation method thereof | |
| CN103526327B (en) | High-modulus low-shrinkage creep-resistant polyester industrial yarn and preparation method thereof | |
| JP3352890B2 (en) | Polylactic acid and method for producing the same | |
| CN113817169A (en) | High-temperature-resistant block polysulfate and preparation method thereof | |
| CN108409949A (en) | A kind of 2,5- furandicarboxylic acids base copolyester material and preparation method thereof | |
| CN117887057A (en) | Scratch-resistant isosorbide type polycarbonate material and preparation method thereof | |
| CN113150244B (en) | Sulfonate type epoxy acrylate resin and preparation method and application thereof | |
| CN116425965B (en) | Flame-retardant copolycarbonate and preparation method thereof | |
| CN113527647B (en) | Liquid crystal polymer, preparation method thereof and liquid crystal polymer film | |
| CN107722203A (en) | A kind of solvent-free method for preparing polyether-ether-ketone |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170714 |
|
| RJ01 | Rejection of invention patent application after publication |