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CN107840925A - A kind of sulfonation gutta-percha preparation method - Google Patents

A kind of sulfonation gutta-percha preparation method Download PDF

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Publication number
CN107840925A
CN107840925A CN201711325023.XA CN201711325023A CN107840925A CN 107840925 A CN107840925 A CN 107840925A CN 201711325023 A CN201711325023 A CN 201711325023A CN 107840925 A CN107840925 A CN 107840925A
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CN
China
Prior art keywords
gutta
percha
sulfonation
eucommia
bark
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.)
Withdrawn
Application number
CN201711325023.XA
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Chinese (zh)
Inventor
杨凤
代丽
张嫚
李元哲
方庆红
康海澜
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Shenyang University of Chemical Technology
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Shenyang University of Chemical Technology
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Application filed by Shenyang University of Chemical Technology filed Critical Shenyang University of Chemical Technology
Priority to CN201711325023.XA priority Critical patent/CN107840925A/en
Publication of CN107840925A publication Critical patent/CN107840925A/en
Withdrawn legal-status Critical Current

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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F253/00Macromolecular compounds obtained by polymerising monomers on to natural rubbers or derivatives thereof
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08CTREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00Chemical modification of rubber
    • C08C19/20Incorporating sulfur atoms into the molecule
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08CTREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00Chemical modification of rubber
    • C08C19/28Reaction with compounds containing carbon-to-carbon unsaturated bonds

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

A kind of sulfonation gutta-percha preparation method, it is related to a kind of method for preparing rubber, bark of eucommia latex solution and sulfonating agent the A aqueous solution is respectively configured first;The A aqueous solution is slowly added dropwise into bark of eucommia latex solution under nitrogen protection, while adds catalyst B, the reaction extremely phase separation at 40 90 DEG C;Product separating, washing and drying, sulfonation gutta-percha is made.Compared with the sulfonating agents such as the concentrated sulfuric acid, sulfur trioxide, such a sulfonating agent is relatively stable, and easy to operation and reaction condition is gentle;Sulfonating reaction heat release is steadily easily-controllable, and side reaction is few, it is not easy to generates gel.The introducing of sulfonate groups can assign gutta-percha hydrophily, dielectricity, shape memory function or self-repair function.The low glass transition temperature of gutta-percha and the flexible high resiliency combination dielectricity and self-repair function assigned of double bond, sulfonation gutta-percha have potential application in fields such as robot soft material, amberplex, flexible sensors.

Description

A kind of sulfonation gutta-percha preparation method
Technical field
The present invention relates to a kind of method for preparing rubber, more particularly to a kind of sulfonation gutta-percha preparation method.
Background technology
Currently, natural rubber shortage of resources situation getting worse;On the other hand, it is right during the production and application of synthetic rubber The influence of the energy and environment progressively causes global attention.In this context, as the distinctive high score child resource in China, gutta-percha Extraction and research for application and development receive much concern, show important application prospect and potential economic value.
The chemical composition of gutta-percha is anti-form-1,4 polyisoprene, flexible chain in its molecular structure, rich in double bond and knot Crystalline substance makes gutta-percha show the integral performance characteristics of rubber and plastic.Because crystalline texture masks the performance of double bond and flexible chain structure, Gutta-percha is presented with rigid plastics under normal temperature.But it will be able to along with the destruction of gutta-percha crystalline texture, the compliance of double bond Embody., can be by carrying out chemical modification to the double bond in gutta-percha to change the crystallization degree of gutta-percha, crystal knot based on this Structure and crystallization distribution, so as to obtain the gutta-percha of different application performance.On the one hand carrying out sulfonation modifying to gutta-percha can adjust The crystallizing power of strand is controlled, so as to regulate and control its mechanical state;On the other hand, the introducing of polarity, hydrophilic sulfonic acid group, and The formation of ion cluster and it is uniformly distributed and can also impart to the distinctive feature of gutta-percha.
The conventional sulfonating agent of rubber sulfonation modifying has a variety of, and simplest is sulfuric acid and sulfur trioxide, but because reaction is acute It is strong, thermal discharge is big, be easily caused rubber decompose or coking [Zhao Xiaowei etc., the progress of sulfonation EP rubbers ionomer, elasticity Body, 2006,16 (5):75-78].Sulfur trioxide and phosphate, amine, the complex of acid amides or carboxylic acid can be kept away to a certain extent Exempt from above mentioned problem.The most frequently used rubber sulfonating agent is the acetylsulfuric acid that sulfuric acid and acetic anhydride are formed in situ, and reaction is gently and conveniently Operation, is widely used in low-unsaturation-degree rubber, such as [Du Juan, sulfonation three in the sulfonating reaction of butyl rubber and ethylene propylene diene rubber The synthesis of first EP rubbers adhesive, elastomer, 2012,22(5):53-54].But for the rubber of high degree of unsaturation, such as along fourth Rubber and isoprene rubber, gel is easily generated when from above-mentioned sulfonating agent sulfonation.
The content of the invention
It is an object of the invention to provide a kind of sulfonation gutta-percha preparation method, the present invention selects reactive small molecule sulphur Sour sodium monomer is sulfonating agent, anti-using the free radical between the methylene of sulfonating agent and gutta-percha main chain double bond or neighbouring double bond Should, sulfonate groups are incorporated into gutta-percha strand, realize the sulfonation modifying to gutta-percha.
The purpose of the present invention is achieved through the following technical solutions:
A kind of sulfonation gutta-percha preparation method, methods described include following preparation process:
The aqueous solution of bark of eucommia latex solution and mass ratio for 5-30 wt% vulcanizing agent A is respectively configured;By the water-soluble of A under nitrogen protection Liquid is slowly added dropwise into bark of eucommia latex solution, and sulfonating agent A dosage is sulfonating agent/double bond mol ratio=0.1:1~0.9:1;Add simultaneously Enter catalyst B, the reaction extremely phase separation at 40-90 DEG C;Product separating, washing and drying, sulfonation gutta-percha is made.
A kind of described sulfonation gutta-percha preparation method, the sulfonating agent A are sodium p styrene sulfonate, ALS With sodium isethionate one or more therein.
A kind of described sulfonation gutta-percha preparation method, the catalyst B are benzoyl peroxide or persulfate.
A kind of described sulfonation gutta-percha preparation method, the sulfonating agent A concentration of aqueous solution are 5-30 wt%.
Advantages of the present invention is with effect:
1. rubber backbone double bond participates in sulfonating reaction, therefore suitable for the rubber sulfonation modifying of high degree of unsaturation;
2. compared with the sulfonating agents such as the concentrated sulfuric acid, sulfur trioxide, such a sulfonating agent is relatively stable, therefore easy to operation and reaction bar Part is gentle;Sulfonating reaction heat release is steadily easily-controllable, and side reaction is few;It is not easy to generate gel.
3. introducing hydrophily, ionic sulfonate groups in nonpolar gutta-percha strand, it is hydrophilic gutta-percha can be assigned Property, dielectricity.What is more important, the presence of ionic bond and invertibity can also assign gutta-percha shape memory or selfreparing work( Can, be advantageous to widen performance/envelop of function of gutta-percha, expand its application field.Such as combine self-repair function, dielectric properties with And the elasticity that the low glass transition temperature of gutta-percha and double bond flexible chain are assigned, sulfonation gutta-percha is in robot software material The fields such as material, amberplex, flexible sensor have potential application.
Brief description of the drawings
Fig. 1 is respectively the infrared spectrogram of Examples 1 and 2 product sulfonation gutta-percha.
Embodiment
With reference to embodiment, the present invention is described in detail.
Embodiment 1
The bark of eucommia latex solution that solid content is 5% and the aqueous solution for the sodium p styrene sulfonate that mass ratio is 10% is respectively configured;Nitrogen The aqueous solution of sodium p styrene sulfonate is added dropwise in bark of eucommia latex solution with the speed of 3s/ drops under protection, while adds catalyst Potassium peroxydisulfate, the reaction extremely phase separation at 60 DEG C;Product separating, washing and drying, sulfonation gutta-percha is made.
Embodiment 2
The bark of eucommia latex solution that solid content is 3% and the aqueous solution for the sodium p styrene sulfonate that mass ratio is 15% is respectively configured;Nitrogen The aqueous solution of SSS is added dropwise in bark of eucommia latex solution with the speed of 3s/ drops under protection, while adds catalyst mistake BP, the reaction extremely phase separation at 75 DEG C;Product separating, washing and drying, sulfonation gutta-percha is made.
Embodiment 3
The bark of eucommia latex solution that solid content is 7.5% and the aqueous solution for the ALS that mass ratio is 5% is respectively configured;Nitrogen is protected The aqueous solution of ALS is added dropwise in bark of eucommia latex solution with the speed of 3s/ drops under shield, while adds catalyst peroxide Change benzoyl, the reaction extremely phase separation at 60 DEG C;Product separating, washing and drying, sulfonation gutta-percha is made.
Embodiment 4
The bark of eucommia latex solution that solid content is 4% and the aqueous solution for the ALS that mass ratio is 10% is respectively configured;Nitrogen is protected The aqueous solution of SSS is added dropwise in bark of eucommia latex solution with the speed of 3s/ drops under shield, while adds catalyst over cure Sour ammonium, the reaction extremely phase separation at 80 DEG C;Product separating, washing and drying, sulfonation gutta-percha is made.
Embodiment 5
The bark of eucommia latex solution that solid content is 3% and the aqueous solution for the sodium isethionate that mass ratio is 25% is respectively configured;Nitrogen is protected The above-mentioned aqueous solution is added dropwise in bark of eucommia latex solution with the speed of 3s/ drops under shield, while adds catalyst benzoyl peroxide, Reaction is extremely separated at 70 DEG C;Product separating, washing and drying, sulfonation gutta-percha is made.
The present invention is described in detail with reference to the accompanying drawings.
Table 1 is respectively the sulfur content of the product sulfonation gutta-percha of embodiment 1,2,3.
Fig. 1 is the IR curves of gutta-percha and Examples 1 and 2 product sulfonation gutta-percha.
Wave number 1252cm-1、1228cm-1The new peak that place occurs belongs to S=O antisymmetric stretching vibration, 1063cm-1Place goes out Existing new peak belongs to S=O symmetrical stretching vibration peak.
Table 1 and Fig. 1 confirm gutta-percha by success sulfonation.

Claims (4)

1. a kind of sulfonation gutta-percha preparation method, it is characterised in that methods described includes following preparation process:
The aqueous solution of bark of eucommia latex solution and mass ratio for 5-30 wt% vulcanizing agent A is respectively configured;By the water-soluble of A under nitrogen protection Liquid is slowly added dropwise into bark of eucommia latex solution, and sulfonating agent A dosage is sulfonating agent/double bond mol ratio=0.1:1~0.9:1;Add simultaneously Enter catalyst B, the reaction extremely phase separation at 40-90 DEG C;Product separating, washing and drying, sulfonation gutta-percha is made.
2. a kind of sulfonation gutta-percha preparation method according to claim 1, it is characterised in that the sulfonating agent A is to benzene Vinyl sulfonic acid sodium, ALS and sodium isethionate one or more therein.
3. a kind of sulfonation gutta-percha preparation method according to claim 1, it is characterised in that the catalyst B is peroxide Change benzoyl or persulfate.
A kind of 4. sulfonation gutta-percha preparation method according to claim 1, it is characterised in that the sulfonating agent A aqueous solution Concentration is 5-30 wt%.
CN201711325023.XA 2017-12-13 2017-12-13 A kind of sulfonation gutta-percha preparation method Withdrawn CN107840925A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108373514A (en) * 2018-01-04 2018-08-07 沈阳化工大学 A kind of sulfonation gutta-percha preparation method
CN108912430A (en) * 2018-07-23 2018-11-30 宁波昊鑫裕隆新材料有限公司 A kind of chlorinated rubber and preparation method and purposes of nanometer additive and Sodium Allyl Sulfonate modified synergic

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1051290A (en) * 1989-10-31 1991-05-15 沃纳-兰伯特公司 Sweetener-flavor delivery systme of sealing and preparation method thereof
CN1052777A (en) * 1989-12-18 1991-07-10 沃纳-兰伯特公司 Multiple encapsulated sweetener delivery system and preparation method thereof
CN103113597A (en) * 2013-01-30 2013-05-22 怡维怡材料研究院有限公司 Continuous manufacturing method of rubber masterbatch and rubber masterbatch prepared by same
CN103203810A (en) * 2013-01-10 2013-07-17 怡维怡材料研究院有限公司 Continuous manufacturing method for rubber masterbatch, rubber masterbatch prepared by using continuous manufacturing method and rubber product
CN104341686A (en) * 2014-11-03 2015-02-11 怡维怡橡胶研究院有限公司 Application of continuously prepared rubber master batch to car tire inner liner rubber
CN104937044A (en) * 2012-10-31 2015-09-23 纳米技术创新公司 Nanotechnological thermal insulating coating and uses thereof
CN107746440A (en) * 2017-09-26 2018-03-02 沈阳化工大学 A kind of sulfonation gutta-percha preparation method

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1051290A (en) * 1989-10-31 1991-05-15 沃纳-兰伯特公司 Sweetener-flavor delivery systme of sealing and preparation method thereof
CN1052777A (en) * 1989-12-18 1991-07-10 沃纳-兰伯特公司 Multiple encapsulated sweetener delivery system and preparation method thereof
CN104937044A (en) * 2012-10-31 2015-09-23 纳米技术创新公司 Nanotechnological thermal insulating coating and uses thereof
CN103203810A (en) * 2013-01-10 2013-07-17 怡维怡材料研究院有限公司 Continuous manufacturing method for rubber masterbatch, rubber masterbatch prepared by using continuous manufacturing method and rubber product
CN103113597A (en) * 2013-01-30 2013-05-22 怡维怡材料研究院有限公司 Continuous manufacturing method of rubber masterbatch and rubber masterbatch prepared by same
CN104341686A (en) * 2014-11-03 2015-02-11 怡维怡橡胶研究院有限公司 Application of continuously prepared rubber master batch to car tire inner liner rubber
CN107746440A (en) * 2017-09-26 2018-03-02 沈阳化工大学 A kind of sulfonation gutta-percha preparation method

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108373514A (en) * 2018-01-04 2018-08-07 沈阳化工大学 A kind of sulfonation gutta-percha preparation method
CN108912430A (en) * 2018-07-23 2018-11-30 宁波昊鑫裕隆新材料有限公司 A kind of chlorinated rubber and preparation method and purposes of nanometer additive and Sodium Allyl Sulfonate modified synergic
CN108912430B (en) * 2018-07-23 2020-09-29 宁波昊鑫裕隆新材料有限公司 Chlorinated rubber synergistically modified by nano additive and sodium allylsulfonate, preparation method and application

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