CN109762121B - Brominated SBS product with low molecular weight and high thermal stability and preparation method thereof - Google Patents
Brominated SBS product with low molecular weight and high thermal stability and preparation method thereof Download PDFInfo
- Publication number
- CN109762121B CN109762121B CN201811612406.XA CN201811612406A CN109762121B CN 109762121 B CN109762121 B CN 109762121B CN 201811612406 A CN201811612406 A CN 201811612406A CN 109762121 B CN109762121 B CN 109762121B
- Authority
- CN
- China
- Prior art keywords
- sbs
- electric field
- product
- molecular weight
- brominated
- 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.)
- Active
Links
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a brominated SBS product with low molecular weight and high thermal stability and a preparation method thereof, and the preparation method comprises the following steps: TBAB dissolution, SBS dissolution, one-step mixing reaction, decoloring and washing, bromine solution preparation and two-step mixing reaction; the one-step mixing reaction is carried out, the temperature of the dissolved SBS is reduced to be below 10 ℃, and an equimolar material I is dripped; the two-step mixed reaction: cooling the material obtained after decoloring and washing to a temperature lower than 10 ℃, and dropwise adding equimolar material II; the brominated SBS product obtained by the method has the advantages of 1% thermal weight loss temperature of 230 ℃, 5% thermal weight loss of 245 ℃, 10% thermal weight loss of 255 ℃, 50% thermal weight loss of 280 ℃, and bromine content of 66%, and the product has low molecular weight, high purity, good thermal stability, difficult curling and winding of the brominated SBS block, low viscosity, simple process, improved conversion rate of reaction, and contribution to popularization and application.
Description
Technical Field
The invention relates to the technical field of fine chemical engineering, in particular to a brominated SBS product with low molecular weight and high thermal stability and a preparation method thereof.
Background
The brominated flame retardant has good flame retardant effect, light stability and antistatic property, and can be widely applied to various plastics such as polyolefin, polyamide and polystyrene, fiber, silicon rubber and other synthetic rubber materials. The content of bromine in the flame retardant system is an important parameter for evaluating the flame retardant performance of the bromine flame retardant, and the quality and the flame retardant effect of the bromine flame retardant are directly influenced by the content of bromine.
Brominated SBS, namely brominated styrene-butadiene block copolymer, is used as a brand new environment-friendly brominated flame retardant and widely applied to waterproof coiled materials and various plastic plates of different types.
Chinese patent No. CN201410590472.7 discloses a brominated styrene/butadiene copolymer flame retardant and a bromination method thereof. The copolymer of the flame retardant is polymerized by brominated styrene monomer and butadiene monomer, wherein in the brominated styrene/butadiene copolymer, brominated aryl of styrene comprises 2-bromostyrene, 4-bromostyrene and 2, 4-dibromostyrene. The manufacturing method comprises the following steps: 1) selecting raw materials: styrene/butadiene copolymer, sodium bromide content 98-99%, chlorine content more than 99%, isobutanol content more than 99%; 2) SBS is added into the enamel reactor and heated and dissolved by isobutanol; 3) adding a sodium bromide solution, introducing an oxidant, stirring in the reaction process, and absorbing the unreacted oxidant by lime milk at the tail part of the reactor; 4) then cooling to room temperature, adding a catalyst, and continuing stirring and heating; 5) and cooling to room temperature and filtering to obtain the target product brominated styrene/butadiene polymer. Although the invention can obtain lower oligomer, the bromine content can also reach 65-70%, the purity of the product is not high, the color of the product is darker, the conversion rate in the reaction process is lower, the productivity is lower, and the invention cannot be practically applied.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a brominated SBS product with low molecular weight and high thermal stability and a preparation method thereof, so as to realize the following purposes:
(1) the preparation method has the advantages of stable and easily obtained raw materials, low cost, simple process and easy operation, and is beneficial to popularization and application;
(2) the brominated SBS product obtained by the preparation method is an addition product, the molecular weight of the product is low, and the purity of the product is high;
(3) the brominated SBS product obtained by the preparation method has good thermal stability and high thermal weight loss temperature;
(4) the brominated SBS product obtained by the preparation method has the advantages that the brominated SBS block is not easy to curl and wind, the viscosity is low, and the conversion rate of the reaction is improved;
(5) the preparation method of the invention can effectively reduce or eliminate the content of high polymers and ultra-high molecular polymers in the copolymer, greatly improve the purity of the brominated SBS product and improve the comprehensive physical and mechanical properties of the brominated SBS copolymer.
In order to realize the purpose of the invention, the invention adopts the following technical scheme:
a brominated SBS product with low molecular weight and high thermal stability is characterized in that the 1% thermal weight loss temperature of the brominated SBS product is 230 ℃, the 5% thermal weight loss temperature is 245 ℃, the 10% thermal weight loss temperature is 255 ℃, the 50% thermal weight loss temperature is 280 ℃, and the bromine content is 66%.
The following is a further optimization of the technical solution:
the brominated SBS product with low molecular weight and high thermal stability is white in appearance at the temperature of 100 ℃ and 160 ℃, and has no plastic feeling in touch.
The low molecular weight and high thermal stability brominated SBS product has a molecular weight of 10000-100000 and a viscosity of 2000-50000cp at 250 ℃.
The invention also provides a preparation method of the brominated SBS product with low molecular weight and high thermal stability,
the preparation method of the low-molecular-weight high-thermal-stability brominated SBS product comprises the following steps of: TBAB dissolution, SBS dissolution, one-step mixing reaction, decoloring and washing, bromine solution preparation, two-step mixing reaction, heat preservation and separation, and extraction.
Dissolving TBAB, namely adding 12.82g of TBAB and 100g g of DCM into a 250ml conical flask, and dissolving to obtain a material (I);
and (3) dissolving the SBS, namely adding 5g of SBS and 100g of DCM into a 500ml four-mouth bottle, wherein the dissolving temperature is normal temperature.
And (3) carrying out one-step mixing reaction, cooling the dissolved SBS to below 10 ℃, and dropwise adding an equimolar material for 1 hour.
Preparation of the bromine solution: br28.7g and DCM100g were added to a 250ml Erlenmeyer flask and the temperature and phenomena were observed; forming a material II.
The two-step mixed reaction: and (3) cooling the temperature of the material obtained after decoloring and washing to be lower than 10 ℃, dropwise adding equimolar material II, and completing dropwise adding within one hour.
The invention also provides a preparation method of the brominated SBS product with low molecular weight and high thermal stability, which is characterized by comprising the preparation of SBS miniemulsion, wherein the preparation of the SBS miniemulsion comprises the following steps:
1) adding 0.25g of co-stabilizer into 5g of commercially available SBS, stirring the mixture under a magnetic stirrer, adding 0.1g of calcium carbonate powder, dispersing and grinding the mixture until D90 is less than or equal to 0.75um, performing ultrasonic-ultraviolet synergistic treatment for 65min under nitrogen flow, wherein the ultrasonic frequency is 55KHz, the power is 425W, the wavelength of ultraviolet light is 385nm, and the flow rate of nitrogen flow is 21 ml/min;
2) treating 500-600 mus by adopting a pulsed electric field with the frequency of 16Hz and the electric field intensity of 12kV/cm to obtain primary electric field treatment liquid;
3) placing the electric field primary treatment liquid in a closed storage tank, adding 0.1g of calcium carbonate powder, mixing, dispersing and grinding until D90 is less than or equal to 0.75um, stirring for 12min under a magnetic stirrer, then treating 980 mus by adopting a pulsed electric field with the frequency of 20Hz and the electric field intensity of 20kV/cm to obtain electric field secondary treatment liquid, and removing the calcium carbonate powder by ultrafiltration treatment;
4) adding emulsifier sodium dodecyl sulfate, and stirring at 7000rad/min for 15min to obtain SBS miniemulsion;
the co-stabilizer is a mixture of styrene and 1, 3-butadiene, and the molar ratio of the styrene to the 1, 3-butadiene is 3: 7;
the molecular formula of the commercially available SBS is (C)6H5C2H3)m(C4H6) n, wherein m: n =3: 7.
The weight average molecular weight of the obtained SBS miniemulsion is 10000-20000.
The invention also provides a brominated SBS product with low molecular weight and high thermal stability, wherein the 1% thermal weight loss temperature of the brominated SBS product with low molecular weight and high thermal stability is 252 ℃, 5% thermal weight loss is 255 ℃, 10% thermal weight loss is 261 ℃, 50% thermal weight loss is 332 ℃, the yield is 97.8%, the molecular weight is 10000-.
The invention has the following beneficial effects:
(1) the preparation method has the advantages of stable and easily obtained raw materials, low cost, simple process and easy operation, and is beneficial to popularization and application;
(2) the brominated SBS product obtained by the preparation method is an addition product, the molecular weight of the product is low, and the purity of the product is high; the molecular weight of the product is 10000-100000;
(3) the brominated SBS product obtained by the preparation method of the invention has good thermal stability and higher thermal weight loss temperature: the temperature of 1% thermal weight loss is 230-252 ℃, the temperature of 5% thermal weight loss is 245-255 ℃, the temperature of 10% thermal weight loss is 255-261 ℃, and the temperature of 50% thermal weight loss is 280-332 ℃;
(4) the brominated SBS product obtained by the preparation method has the advantages that the brominated SBS block is not easy to curl and wind, the viscosity is low, and the conversion rate of the reaction is improved; viscosity of 2000-50000 cp;
(5) the preparation method of the invention can effectively reduce or eliminate the content of high polymers and ultra-high molecular polymers in the copolymer, greatly improve the purity of the brominated SBS product and improve the comprehensive physical and mechanical properties of the brominated SBS copolymer.
Detailed Description
The following examples are further detailed descriptions of the present invention.
Example 1: brominated SBS product with low molecular weight and high thermal stability and preparation method thereof
1. Dissolution of TBAB: TBAB12.82g and DCM100g were added to a 250ml Erlenmeyer flask and the temperature and phenomena were observed; forming a material I, namely vintage tetrabutylammonium tribromide;
2. dissolution of SBS: SBS 5g + DCM100g (determined according to Br-SBS solubility) is added into a 500ml four-mouth bottle, and the dissolving temperature is normal temperature;
3. one-step mixing reaction: after SBS is dissolved, dropwise adding equimolar materials (I) at the temperature of lower than 10 ℃, and completing dropwise adding within one hour;
4. and (3) finishing the reaction: after the dropwise addition is finished, preserving the heat for 1 hour, and adding 10% sodium bisulfite solution to finish the reaction after the reaction is completed;
5. decoloring and washing: adding 200.0g of 10% sodium bisulfite solution for decoloring, removing bromine and adjusting the value to be neutral; separating with separating funnel to obtain organic phase, washing with 200g deionized water for three times;
6. preparation of bromine solution: adding Br2 8.7g and DCM100g were added to a 250ml Erlenmeyer flask and the temperature and phenomena were observed; forming a material II, namely wine red bromine solution;
7. two-step mixing reaction: cooling the temperature of the material in the step 5 to be lower than 10 ℃, dropwise adding equimolar material II, and completing dropwise adding within one hour;
8. and (3) heat preservation: after the dropwise addition is finished, preserving the heat for 1 hour;
9. separation: separating with separating funnel to obtain organic phase, decolorizing with 10% sodium bisulfite solution to remove bromine, and adjusting to neutral; adding toluene with the same mass as DCM, separating an organic phase, washing with 200g of deionized water, and washing for three times;
10. and (3) extraction: extracting with methanol, separating, and drying to obtain the final product.
The product indexes of the brominated SBS product with low molecular weight and high thermal stability obtained by the embodiment of the invention are as follows:
example 2: brominated SBS product with low molecular weight and high thermal stability and preparation method thereof
1. TBAB12.82g and DCM100g are added into a 250ml conical flask, and the temperature and phenomenon are observed to form a material (i) namely wine red tetrabutylammonium tribromide;
2. preparation of SBS miniemulsion:
1) adding 0.25g of co-stabilizer into 5g of commercially available SBS, stirring the mixture under a magnetic stirrer, adding 0.1g of calcium carbonate powder, dispersing and grinding the mixture until D90 is less than or equal to 0.75um, performing ultrasonic-ultraviolet synergistic treatment for 65min under nitrogen flow, wherein the ultrasonic frequency is 55KHz, the power is 425W, the wavelength of ultraviolet light is 385nm, and the flow rate of nitrogen flow is 21 ml/min;
in this example, the commercially available SBS is of the formula (C)6H5C2H3)m(C4H6) n, wherein m: n =3: 7;
the co-stabilizer is a mixture of styrene and 1, 3-butadiene, and the molar ratio of the styrene to the 1, 3-butadiene is 3: 7;
2) treating 500-600 mus by adopting a pulsed electric field with the frequency of 16Hz and the electric field intensity of 12kV/cm to obtain primary electric field treatment liquid;
3) placing the electric field primary treatment liquid in a closed storage tank, adding 0.1g of calcium carbonate powder, mixing, dispersing and grinding until D90 is less than or equal to 0.75um, stirring for 12min under a magnetic stirrer, then treating 980 mus by adopting a pulsed electric field with the frequency of 20Hz and the electric field intensity of 20kV/cm to obtain electric field secondary treatment liquid, and removing the calcium carbonate powder by ultrafiltration treatment;
4) adding emulsifier sodium dodecyl sulfate, and stirring at 7000rad/min for 15min to obtain SBS miniemulsion;
the SBS miniemulsion obtained is analyzed by gel chromatography, and the weight average molecular weight range is 10000-.
3. Adding 100g of DCM into the SBS miniemulsion obtained in the step, stirring, transferring to a 500ml four-mouth bottle, dissolving at normal temperature, rapidly cooling to 8-12 ℃, wherein the cooling rate is 3 ℃/min, dropwise adding an equimolar material I, and completing dropwise adding within one hour;
4. after the dropwise addition is finished, preserving the heat for 1 hour, adding a 10% sodium bisulfite solution, and finishing the reaction;
according to the practical statistics of the inventor, the conversion rate of the step is 97.8%.
5. Adding 200.0g of 10% sodium bisulfite solution for decoloring, removing bromine and adjusting the value to be neutral; separating with separating funnel to obtain organic phase, washing with 200g deionized water for three times;
6. adding Br2 8.7g and DCM100g were added to a 250ml Erlenmeyer flask and the temperature and phenomena were observed; forming a material II, namely wine red bromine solution;
7. cooling the material temperature in the step 5 to be lower than 11-12 ℃, dripping equimolar material II within one hour,
8. after the dropwise addition is finished, preserving the heat for 1 hour;
9. separating with separating funnel to obtain organic phase, decolorizing with 10% sodium bisulfite solution to remove bromine, and adjusting to neutral; adding toluene with the same mass as DCM, separating an organic phase, washing with 200g of deionized water, and washing for three times;
10. extracting with methanol, separating, and drying to obtain the final product.
The product indexes of the brominated SBS product with low molecular weight and high thermal stability obtained by the embodiment of the invention are as follows:
in addition, the inventors of the present invention unexpectedly found that the brominated SBS product with low molecular weight and high thermal stability obtained in example 2 of the present invention has improved comprehensive physical and mechanical properties, more stable morphology, reduced surface tension, and excellent compatibility when combined with a plate substrate, and can obtain the effect of adding a compatibility aid to a conventional brominated SBS product without adding any other aid for promoting compatibility, which greatly saves process costs, and is unexpected by those skilled in the art.
Unless otherwise stated, the percentages used in the present invention are percentages by weight, and the proportions described in the present invention are proportions by mass.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (1)
1. A method for preparing a brominated SBS product having a low molecular weight and a high thermal stability, the method comprising the steps of:
step 1, TBAB12.82g, Br2Adding DCM100g into a 250ml conical flask, and observing the temperature and phenomenon to form a material (i) namely wine red tetrabutyl ammonium tribromide;
step 2, preparation of SBS miniemulsion:
1) adding 0.25g of co-stabilizer into 5g of commercially available SBS, stirring the mixture under a magnetic stirrer, adding 0.1g of calcium carbonate powder, dispersing and grinding the mixture until the D90 is less than or equal to 0.75 mu m, performing ultrasonic-ultraviolet synergistic treatment for 65min under nitrogen flow, wherein the ultrasonic frequency is 55KHz, the power is 425W, the wavelength of ultraviolet light is 385nm, and the flow rate of nitrogen flow is 21 mL/min;
the molecular formula of the commercially available SBS is (C)6H5C2H3)m(C4H6) n, wherein m: n =3: 7;
the co-stabilizer is a mixture of styrene and 1, 3-butadiene, and the molar ratio of the styrene to the 1, 3-butadiene is 3: 7;
2) treating 500-600 mus by adopting a pulsed electric field with the frequency of 16Hz and the electric field intensity of 12kV/cm to obtain primary electric field treatment liquid;
3) placing the electric field primary treatment liquid in a closed storage tank, adding 0.1g of calcium carbonate powder, mixing, dispersing and grinding until D90 is less than or equal to 0.75 mu m, stirring for 12min under a magnetic stirrer, then treating 980 mu s by adopting a pulsed electric field with the frequency of 20Hz and the electric field strength of 20kV/cm to obtain electric field secondary treatment liquid, and removing the calcium carbonate powder by ultrafiltration treatment;
4) adding emulsifier sodium dodecyl sulfate, and stirring at 7000rad/min for 15min to obtain SBS miniemulsion;
the obtained SBS miniemulsion is analyzed by gel chromatography, and the weight average molecular weight range is 10000-;
step 3, adding 100g of DCM into the SBS miniemulsion obtained in the step, stirring, transferring to a 500ml four-mouth bottle, dissolving at normal temperature, rapidly cooling to 8-12 ℃, wherein the cooling rate is 3 ℃/min, dropwise adding an equimolar material I, and completing dropwise adding within one hour;
step 4, after the dropwise addition is finished, preserving the heat for 1 hour, adding 10wt% of sodium bisulfite solution, and finishing the reaction;
the conversion rate in this step was 97.8%;
step 5, adding 200.0g of 10wt% sodium bisulfite solution for decoloring and removing bromine, and adjusting the solution to be neutral; separating with separating funnel to obtain organic phase, washing with 200g deionized water for three times;
step 6, adding Br28.7g and DCM100g plusPutting into a 250ml conical flask, and observing the temperature and the phenomenon; forming a material II, namely wine red bromine solution;
step 7, cooling the temperature of the materials in the step 5 to be lower than 11 ℃, dropwise adding equimolar materials II within one hour,
step 8, after the dropwise addition is finished, preserving the heat for 1 hour;
step 9, separating by using a separating funnel to obtain an organic phase, decoloring and removing bromine by using a 10wt% sodium bisulfite solution, and adjusting the value to be neutral; adding toluene with the same mass as DCM, separating an organic phase, washing with 200g of deionized water, and washing for three times;
and step 10, extracting with methanol, separating and drying to obtain the product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811612406.XA CN109762121B (en) | 2018-12-27 | 2018-12-27 | Brominated SBS product with low molecular weight and high thermal stability and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811612406.XA CN109762121B (en) | 2018-12-27 | 2018-12-27 | Brominated SBS product with low molecular weight and high thermal stability and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109762121A CN109762121A (en) | 2019-05-17 |
| CN109762121B true CN109762121B (en) | 2021-07-30 |
Family
ID=66452115
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811612406.XA Active CN109762121B (en) | 2018-12-27 | 2018-12-27 | Brominated SBS product with low molecular weight and high thermal stability and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109762121B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007058736A1 (en) * | 2005-11-12 | 2007-05-24 | Dow Global Technologies Inc. | Brominated butadiene/vinyl aromatic copolymers, blends of such copolymers with a vinyl aromatic polymer, and polymeric foams formed from such blends |
| CN102015774A (en) * | 2008-05-01 | 2011-04-13 | 陶氏环球技术公司 | Two-step process for brominating butadiene copolymers |
| CN104327214A (en) * | 2014-10-29 | 2015-02-04 | 青岛方泰克新材料有限公司 | Brominated styrene/butadiene copolymer fire retardant and bromination method thereof |
| CN106565876A (en) * | 2016-11-01 | 2017-04-19 | 珠海澳圣聚合物材料有限公司 | Continuous preparation method of controlled-molecular-weight brominated polystyrene |
-
2018
- 2018-12-27 CN CN201811612406.XA patent/CN109762121B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007058736A1 (en) * | 2005-11-12 | 2007-05-24 | Dow Global Technologies Inc. | Brominated butadiene/vinyl aromatic copolymers, blends of such copolymers with a vinyl aromatic polymer, and polymeric foams formed from such blends |
| CN102015774A (en) * | 2008-05-01 | 2011-04-13 | 陶氏环球技术公司 | Two-step process for brominating butadiene copolymers |
| CN104327214A (en) * | 2014-10-29 | 2015-02-04 | 青岛方泰克新材料有限公司 | Brominated styrene/butadiene copolymer fire retardant and bromination method thereof |
| CN106565876A (en) * | 2016-11-01 | 2017-04-19 | 珠海澳圣聚合物材料有限公司 | Continuous preparation method of controlled-molecular-weight brominated polystyrene |
Non-Patent Citations (2)
| Title |
|---|
| 六溴环十二烷替代品-溴化丁二烯共聚物合成研究;吴多坤等;《山东化工》;20161231;第45卷(第17期);18-20、24 * |
| 环保型溴系阻燃剂研究进展;田赪等;《工程塑料应用》;20180930;第46卷(第9期);142-147 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109762121A (en) | 2019-05-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106146720B (en) | Alcoholysis method in preparation process of ethylene-vinyl alcohol copolymer | |
| KR100360173B1 (en) | Block copolymers with improved combination of properties | |
| CN105236798A (en) | Preparation method of naphthalene-series water reducing agent | |
| CN107709374B (en) | Process for producing halogenated isoolefin polymer | |
| CN114957517B (en) | Method for continuously producing brominated polystyrene | |
| CN101935370A (en) | Method for preparing polyvinylpolypyrrolidone | |
| CN109762121B (en) | Brominated SBS product with low molecular weight and high thermal stability and preparation method thereof | |
| CN111019136A (en) | Environment-friendly method for producing MQ silicon resin | |
| CN104194031B (en) | A kind of preparation method of the expandable polystyrene granule containing fire retardant | |
| TW201841947A (en) | Production method for polymer, compound containing radical-polymerization initiation group, and polymer | |
| CN109762120B (en) | Brominated SBS product with narrow molecular weight distribution and high thermal stability and preparation method thereof | |
| CN109053389B (en) | Synthetic method of 2,4, 6-tribromophenyl allyl ether | |
| CN106188400B (en) | A kind of preparation process of polystyrene multi-component copolymer high molecular material | |
| CN104194182A (en) | PVC/PVC-g-DMC antibacterial plastic and preparation technology thereof | |
| CN110963939A (en) | Preparation method of C16 side chain substituted fluorine-containing diamine monomer | |
| CN101215251A (en) | Method for preparing 3,4-dichlorobenzoperoxide | |
| CN110963938A (en) | Preparation method of C15 side chain substituted fluorine-containing diamine monomer | |
| CN105348443A (en) | Catalytic system for synthesizing piperylene petroleum resin and preparation method for piperylene petroleum resin | |
| Fraga Domínguez et al. | Controlled synthesis of poly (neopentyl p‐styrene sulfonate) via reversible addition‐fragmentation chain transfer polymerisation | |
| CN106317306B (en) | A kind of preparation method of cationic polyacrylamide | |
| CN109553714B (en) | Preparation method of oligomer for improving wet skid resistance of rubber | |
| CN110003446B (en) | Light-color high-softening-point terpene-phenol resin and preparation method and application thereof | |
| CN102443103A (en) | Preparation method of low-chroma high-softening-point dicyclopentadiene petroleum resin | |
| CN108047448B (en) | Bismaleimide polymer and preparation method thereof | |
| CN105175714A (en) | Process method for preparing cyano polyetherketoneketone resin |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP03 | Change of name, title or address |
Address after: 262714 Shouguang Yangkou Chemical Industrial Park, Weifang City, Shandong Province (West of Yanglin road and north of Donghai Road) Patentee after: Shandong XURUI New Material Co.,Ltd. Address before: 262714 Bohai Industrial Park, Yangkou Town, Shouguang City, Weifang City, Shandong Province Patentee before: SHANDONG SUNRIS CO.,LTD. |
|
| CP03 | Change of name, title or address | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: A low molecular weight and high thermal stability brominated SBS product and its preparation method Effective date of registration: 20230815 Granted publication date: 20210730 Pledgee: Zhejiang Commercial Bank Co.,Ltd. Weifang branch Pledgor: Shandong XURUI New Material Co.,Ltd. Registration number: Y2023980052362 |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right |