CN105111373B - The preparation method and products therefrom of a kind of isoprene functional rubber of oil resistant - Google Patents
The preparation method and products therefrom of a kind of isoprene functional rubber of oil resistant Download PDFInfo
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Abstract
The present invention proposes a kind of preparation method of the isoprene functional rubber of oil resistant, including step S1：Water, emulsifying agent, electrolyte, monomer are added in reactor as polymerization system, carry out pre-emulsification reaction；S2, into gained pre-emulsification solution initiator is added, reaction 2~7 hours is carried out in a nitrogen atmosphere, the first reaction solution is obtained；S3, using calcium chloride solution to the first reaction solution carry out demulsification coagulate rubber, obtain isoprene limonene ester terpolymer rubber.The present invention also proposes the terpolymer rubber preparation method of hydrogenation.The present invention is from molecular structure, by introducing second party rigid unitary limonene, third party's polar monomer butyl acrylate and dibutyl itaconate, by ternary emulsion copolymerization, obtained ternary polymerization elastomer realizes the breakthrough of isoprene rubber oil resistivity and wearability, it is further advanced by hydrogenation, the unsaturated carbon-carbon double bond in part is eliminated, the synchronous raising of isoprene rubber heat resistance and ozone resistance is realized.
Description
Technical field
The invention belongs to field of organic polymer compound, and in particular to a kind of isoprene ternary rubber preparation method and
Products therefrom.
Background technology
Isoprene rubber is a kind of general purpose rubber synthesized by isoprene for matrix, due to similar to natural rubber
Chemical composition, so with good elasticity, cold resistance and high tensile strength.Be substitute natural rubber manufacture passenger tyre,
The important source material of bias tire, radial heavy duty tire, half steel car and light truck radial etc., can also be widely used in producing curtain
Cloth glue, conveyer belt, machinework, sebific duct, adhesive tape, sponge, adhesive, electric wire, sports apparatus, medical material and rubber overshoes
Deng field.It can be used alone, and can also be used in combination with natural rubber or other synthetic rubber.
Although isoprene rubber has many excellent performances, simultaneously there is also some shortcomings, such as oil resistivity is poor, wear-resisting
The bad, anti-slippery of property, rolling resistance performance are inadequate, need to be improved in the performance in terms of heat-resisting weatherability, and this is also straight
Connect and have impact on further applying for it.In order to improve the shortcoming of isoprene rubber, its application field, domestic and international researcher are widened
Different modifications have been carried out to it for its different shortcoming.
Wang Jing uses n-BuLi as initiator, has been made that a kind of molecular weight is big, molecular weight distribution by anion method
Narrow butadiene and the copolymer rubber of isoprene, and have studied its crystallization behavior (anionic polymerization method butadiene/isoamyl two
Alkene random copolymerization rubber is synthesized and crystallization behavior research, Wang Jing, Beijing University of Chemical Technology).Cong Hailin etc. is to trans 1,4 poly- isoamyls two
Alkene has carried out epoxidation, improves the rigidity and polarity of polymer molecular chain, but its processing and physical and mechanical properties variation (epoxy
Change the structure and performance of trans-1,4-iroprene polymer, China Synthetic Rubber Industry, 2003).Huangping is poly- using RAFT living radicals
Styrene-isoprene-N- butyl maleimide triblock copolymers have been made in conjunction, and the elastomer has good heat resistance
And wearability.(synthesis and its self assembly research of new PNBMI-b-PS-b-PI triblock copolymers, Huangping, University Of Xiangtan).
But all it is the performance in a certain respect of single improvement isoprene rubber, in other words at it in these current methods
Also it has been short of in his some big links and performance.Therefore, it there is a perceived need to find a kind of system of new isoprene rubber at present
Preparation Method, can more synthetically solve the weak point present in above-mentioned isoprene rubber, especially solve in current isoprene rubber
Existing anti-wear performance is poor, and oil resistivity is bad, be also short of in terms of heat-resisting weather resistance in terms of the problem of.
The content of the invention
The purpose of the present invention is intended to from molecular structure on, by introducing second party rigid unitary and third party's polarity list
Body carries out the method for ternary polymerization to improve the oil resistivity and mechanical property of isoprene rubber, then by complex functionality rubber
It is hydrogenated with, eliminates part unsaturated double-bond further to improve its heat resistance and ozone-resistant aging property, having prepared has
Preferable oil resistivity and mechanical property, the isoprene functional rubber of excellent combination property, further expand isoprene rubber
Application field and application.
The technical scheme for realizing above-mentioned purpose of the present invention is：
A kind of preparation method of the isoprene functional rubber of oil resistant, including step：
S1：Deionized water, emulsifying agent, electrolyte, monomer are added sequentially in reactor as polymerization system, in nitrogen gas
Under atmosphere, polymerization system is heated to 20~60 DEG C, pressurization 0~3Mpa progress pre-emulsification reactions, pre-emulsification solution is obtained；Wherein institute
Monomer is stated for isoprene, limonene and butyl ester, the butyl ester is butyl acrylate or dibutyl itaconate (CAS 2155-
60-4)；
S2, into gained pre-emulsification solution add initiator, in a nitrogen atmosphere, be heated to 50~80 DEG C, pressurization 1~
4Mpa carries out reaction 2~7 hours, obtains the first reaction solution；
S3, using calcium chloride solution to the first reaction solution carry out demulsification coagulate rubber, cleaned with deionized water, dry, obtain
(marked to isoprene-limonene -ester terpolymer rubber with PLIB or PLID).
Wherein, the mass ratio of isoprene, limonene and butyl ester is 30~60 in the monomer：30：10-40；Monomer
Gross mass is the 30~50% of polymerization system；The pre-emulsification time is 0.5~2.0 hour in S1.
Further, also include after S3：
S4：Isoprene-limonene -ester terpolymer rubber is dissolved with solvent, rubber solutions are obtained；
S5：Rubber solutions, catalyst are added sequentially in pressure reaction still, in a hydrogen atmosphere, heating pressurization is carried out
Reaction, is hydrogenated with to rubber, obtains the second reaction solution；
S6：Demulsification is carried out to the second reaction solution using absolute ethyl alcohol and coagulates rubber, is then cleaned, dried with deionized water,
(product is two kinds of isoamyls two labeled as HPLIB or HPLID to the isoprene hydrogenated-limonene -ester terpolymer rubber
Olefinic functionality rubber).
Preferably, in the S1；The emulsifying agent is neopelex or calcium dodecyl benzene sulfonate, emulsifying agent
Quality accounts for the 1~3% of monomer gross mass, and the electrolyte is potassium chloride and/or potassium phosphate, and electrolyte quality accounts for monomer gross mass
0.5~1.0%.
It is highly preferred that the electrolyte be potassium chloride and potassium phosphate, potassium chloride quality account for monomer gross mass 0.4~
0.6%, potassium phosphate quality accounts for the 0.1~0.4% of monomer gross mass.
Wherein, initiator is potassium peroxydisulfate in the S2, and initiator quality accounts for the 0.1~0.5% of monomer gross mass, preferably
For 0.2%.
It is demulsified in the S3 and coagulates rubber and use the existing way in this area, mass fraction can be used for 1~5%
Calcium chloride solution carries out demulsification and coagulates rubber.
Wherein, solvent is dimethylbenzene in the S4, and the mass concentration of the rubber solutions is 2~5%.
Wherein, 80~150 DEG C are heated in the S5, are forced into 1~4MPa, reacted 2~12 hours, obtain the second reaction
Liquid.
Preferably, catalyst is one kind in rhodium, ruthenium, palladium catalyst in the S5, and the addition of catalyst accounts for described different
The 0.05~0.5% of pentadiene-limonene -ester terpolymer rubber quality.
Product made from preparation method proposed by the present invention
The beneficial effects of the present invention are：
The present invention is by by isoprene (IP), limonene (LIM) and butyl acrylate (BA) or dibutyl itaconate
(DBI) copolymerization, further by method of the gained copolymer by solution hydrogenation, elimination portion are carried out by the method for emulsion polymerization
Divide unsaturated double-bond, obtained isoprene functional rubber has good oil resistivity, heat resistance and ozone-resistant aging property.
Apply the technical scheme of the present invention, from molecular structure on, by introducing second party rigid unitary limonene (lemon
Lemon alkene is a kind of natural macromolecular material, can extract and obtain from plant, and it has unique lemonene and special hexa-atomic
Ring structure, can increase the rigidity of polymer molecular chain with isoprene copolymer, so as to improve its isoprene rubber wearability
And tensile property), (butyl acrylate and dibutyl itaconate are all for third party's polar monomer butyl acrylate and dibutyl itaconate
It is the moderate polar monomer of polarity, their addition can influence isoprene Chain Flexibility by a small margin, only loss part
On the premise of glass transition temperature, the oil resistivity of isoprene rubber is improved).By ternary emulsion copolymerization, obtained ternary
Copolymer elastomer realizes the breakthrough of isoprene rubber oil resistivity and wearability, is further advanced by hydrogenation, eliminates part not
Saturation carbon-carbon double bond, realizes the synchronous raising of isoprene rubber heat resistance and ozone resistance.Using the technical side of the present invention
Case, is successfully realized the functionalization of isoprene rubber, realizes the raising of isoprene rubber combination property, has broken isoamyl
Rubber is single due to structure function, and applies situation limited always.
The prenyl functional rubber obtained using preparation method of the present invention, it is in rubber tyre, and automobile sealed circle is defeated
Send the fields such as band that all there is potential application value, and it is in tensile strength, wearability, heat resistance and ozone-resistant aging property
On be superior to isoprene rubber prepared by existing emulsion polymerization.
Brief description of the drawings
The nucleus magnetic hydrogen spectrum figure that Fig. 1 is ternary polymerization product PLIB in embodiments of the invention 1；
Fig. 2 is embodiments of the invention 3 (PLIB) and embodiment 12 (HPLIB), embodiment 11 (PLID) and embodiment 13
(HPLID) the nucleus magnetic hydrogen spectrum figure of synthesis isoprene functional rubber and its hydrogenation products；Wherein Fig. 2 (a) is embodiment 3
(PLIB) and embodiment 12 (HPLIB), Fig. 2 (b) is embodiment 11 (PLID) and embodiment 13 (HPLID).
The oil resistance and IR comparison diagram of isoprene functional rubber prepared by Fig. 3 present invention.
Embodiment
Now illustrate the present invention with following examples, but be not limited to the scope of the present invention.
Used main agents and raw material are as follows in experiment：Deionized water prepared by ion exchange；Detergent alkylate sulphur
Sour sodium (SDBS), analyzes pure；KCl, is analyzed pure；K3PO4, analyze pure；Potassium peroxydisulfate (K2S2O8), analyze pure, butyl acrylate
(BA) pure, the positive ester (DBI) of itaconic acid two, is analyzed, pure, limonene (LIM) is analyzed, pure, monomer isoprene (IP), analysis is analyzed
It is pure, purified using preceding through vacuum distillation.
The means used in embodiment, unless otherwise instructed, using the conventional means in this area.
Embodiment 1：
1) by deionized water, emulsifying agent neopelex (SDBS), electrolyte KCl and K3PO4, monomer be isoamyl
Diene (IP), limonene (LIM) and butyl acrylate (BA), above-mentioned substance is added sequentially in pressure reaction still, is polymerize
System.
Wherein, the deionized water of addition be 250g, monomer gross mass 100g, isoprene (IP), limonene (LIM) and
Butyl acrylate (BA) mass ratio is 6:3:1.SDBS addition accounts for the 2% of monomer gross mass, and the quality of potassium chloride accounts for monomer
The 0.5% of gross mass, the quality of potassium phosphate accounts for the 0.2% of monomer gross mass.The total matter of addition monomer of initiator potassium persulfate
The 0.2% of amount.
2) reactor containing polymerization system is handled, uses N2Pump drainage 5 times, excludes the air in reactor.Then will be anti-
Answer kettle to be heated to 30 DEG C, the pressure in reactor is adjusted to 1MPa, in N2Pre-emulsification 1 hour under atmosphere, obtains pre-emulsification solution.
Pre-emulsification solution is continuously heating to 70 DEG C, reacted 6 hours, after question response terminates, the chlorination for being 4wt% with concentration
Calcium solution demulsification coagulates rubber, is cleaned repeatedly through deionized water, and isoprene-limonene -ester ternary polymerization production is obtained after drying
Thing, labeled as PLIB.
The copolymerization product PLIB prepared in embodiment 1 is characterized.
1st, nucleus magnetic hydrogen spectrum is characterized
Using Bruker AV400 400MHz nuclear magnetic resonance spectrometers, nuclear-magnetism hydrogen is carried out with deuterochloroform dissolving copolymerization product
Stave is levied, as a result as shown in Figure 1.
2nd, the measure of molecular weight
3mg copolymerization products are dissolved in 1ml tetrahydrofurans, determined after being completely dissolved with gel permeation chromatograph (GPC)
The molecular weight of product (molecular weight is 51000).
Embodiment 2
1) by deionized water, emulsifying agent neopelex (SDBS), electrolyte KCl and K3PO4, monomer isoamyl two
Alkene (IP), limonene (LIM) are added sequentially in pressure reaction still with dibutyl itaconate (DBI), obtain polymerization system.
Wherein, the deionized water of addition be 250g, monomer gross mass 100g, isoprene (IP), limonene (LIM) and
Dibutyl itaconate (DBI) mass ratio is 6:3:1.SDBS addition accounts for the 2% of monomer gross mass, and the quality of potassium chloride accounts for list
The 0.5% of body gross mass, the quality of potassium phosphate accounts for the 0.2% of monomer gross mass.The addition monomer of initiator potassium persulfate is total
The 0.2% of quality.
2) reactor containing polymerization system is handled, uses N2Pump drainage 5 times, excludes the air in reactor.Then will be anti-
Answer kettle to be heated to 30 DEG C, the pressure in it is adjusted to 1MPa, in N2Pre-emulsification 1 hour under atmosphere, obtains pre-emulsification solution.
Pre-emulsification solution is continuously heating to 70 DEG C, reacted 6 hours, after question response terminates, the chlorination for being 4wt% with concentration
Calcium solution demulsification coagulates rubber, is cleaned repeatedly through deionized water, copolymerization product PLID is obtained after drying.
Embodiment 3-6
In order to study influence of the different rate of charges to copolymerization product PLIB, selection monomer total number is 100 parts, fixed lemon
The mass fraction of alkene is 30 parts, and butyl acrylate feeds intake respectively 10 parts, 20 parts, 30 parts, 40 parts, and other reaction conditions are：It is single
Body gross mass is 100g, deionized water 200g, SDBS 2g, KCl 0.5g, K3PO40.2g、K2S2O80.25g。
By above-mentioned polymerization system in 30 DEG C and 1MPa N2Pre-emulsification 1 hour under atmosphere, then heats to 70 DEG C, reaction 8
Hour.After reaction terminates, the calcium chloride solution for being 2wt% with concentration demulsification coagulates rubber, is cleaned repeatedly through deionized water, dries
After obtain copolymerization product.
The situation of change changed with rate of charge is constituted using nuclear-magnetism measuring and calculation PLIB copolymerization and determines its molecular weight
Situation refers to table 1.
Table 1：IP/BA feeds intake influence of the composition to PLIB
Embodiment 7-10
In order to study influence of the different rate of charges to copolymerization product PLID, selection monomer total number is 100 parts, fixed lemon
The mass fraction of alkene is 30 parts, and dibutyl itaconate feeds intake respectively 10 parts, 20 parts, 30 parts, 40 parts, and other reaction conditions are：
Monomer gross mass is 100g, deionized water 200g, SDBS 2g, KCl 0.5g, K3PO40.2g、K2S2O80.25g。
By above-mentioned polymerization system in 30 DEG C and 1MPa N2Pre-emulsification 1 hour under atmosphere, then heats to 70 DEG C, reaction 8
Hour.After reaction terminates, the calcium chloride solution for being 2wt% with concentration demulsification coagulates rubber, is cleaned repeatedly through deionized water, dries
After obtain copolymerization product.
The situation of change changed with rate of charge is constituted using nuclear-magnetism measuring and calculation PLID copolymerization and determines its molecular weight
Situation refers to table 2.
Table 2：IP/DBI feeds intake influence of the composition to PLID
Embodiment 11
The composition and conversion ratio of copolymerization product are influenceed in order to study the reaction time, the selection PLID mass ratioes that feed intake are 60/
30/10, the reaction time is 2h, 3h, 4h, 5h, 6h, 8h, 12h.
Other reaction conditions：Deionized water 200g, SDBS 2g, KCl 0.5g, K3PO40.2g、K2S2O80.25g.As a result
As shown in table 3.
Influence of the reaction time of table 3. to copolymerization product PLID copolymerization composition and conversion ratio
Embodiment 12
1) by ternary polymerization product PLIB rubber solutions, catalyst is added sequentially in pressure reaction still, is polymerize
System.
Wherein, using the PLIB of embodiment 3, using dimethylbenzene as solution, it is made into 3wt% glue.The glue of addition is
2L, the rhodium catalyst consumption of addition is 0.06g.
2) reactor containing polymerization system is handled, uses N2Pump drainage 5 times, excludes the air in reactor.Then will be anti-
Answer kettle to be heated to 120 DEG C, be passed through hydrogen, the pressure in reactor is adjusted to 4MPa, react 7 hours.After question response terminates, second is used
Alcoholic solution carries out flocks, is cleaned repeatedly through deionized water, copolymerization product HPLIB is obtained after drying.
Embodiment 13
1) ternary polymerization product PLID rubber solutions, catalyst are added sequentially in pressure reaction still, polymerize
System.
Wherein, using the PLID of embodiment 11, using dimethylbenzene as solvent, it is made into 3wt% glue.The glue of addition is
2L, the rhodium catalyst consumption of addition is 0.06g.
2) reactor containing polymerization system is handled, uses N2Pump drainage 5 times, excludes the air in reactor.Then will be anti-
Answer kettle to be heated to 120 DEG C, be passed through hydrogen, the pressure in reactor is adjusted to 4MPa, react 7 hours.After question response terminates, second is used
Alcoholic solution carries out flocks, is cleaned repeatedly through deionized water, copolymerization product HPLID is obtained after drying.To embodiment 3,11,12,13
Product carry out nuclear-magnetism sign, as shown in Figure 2.Top is embodiment 3 in Fig. 2 (a), and lower section is embodiment 12；Above Fig. 2 (b)
It is that embodiment 11 is reacted 12 hours, lower section is the nuclear magnetic spectrogram of the product of embodiment 14.
In order to contrast IR and the isoprene functional rubber of several synthesis mechanical property, IR (isoprene rubber, emulsion are selected
Polymerization is made, and number-average molecular weight is the sample HPLIB in sample P LIB 57000), in embodiment 3, embodiment 11, is implemented
Sample HPLID in sample P LID in example 12, embodiment 13 is kneaded according to the formula of table 4, vulcanized, and tests vulcanization production
The mechanical property and oil resistance of thing, as a result as shown in table 5, Fig. 3.
The mixing formula of table 4.
The mechanical property of the sulfur product of table 5.
Using technical scheme, mechanical property and the preferable four kinds of isoprene function rubber of wearability have been obtained
Glue.As can be seen from Table 5, HPLIB and HPLID tensile strength, elongation at break, hardness and wear resistance are superior to IR.PLIB、
PLID tensile properties are poor compared with IR.
From figure 3, it can be seen that IR all dissolvings in 3# oil.No matter in 1# oily (IRM901) or 3# oil
(IRM903) in, the mass change of the isoprene functional rubber of four kinds of synthesis is respectively less than IR, the isoprene function of synthesis
The oil resistivity of rubber is superior to IR.
Embodiment above is only that the preferred embodiment of the present invention is described, and not the scope of the present invention is entered
Row is limited, on the premise of design spirit of the present invention is not departed from, technical side of this area ordinary skill technical staff to the present invention
In all variations and modifications that case is made, the protection domain that claims of the present invention determination all should be fallen into.
Claims (9)
1. the preparation method of the isoprene functional rubber of a kind of oil resistant, it is characterised in that including step：
S1：Deionized water, emulsifying agent, electrolyte, monomer are added sequentially in reactor as polymerization system, in nitrogen atmosphere
Under, polymerization system is heated to 20~60 DEG C, pressurization 0~3MPa progress pre-emulsification reactions, pre-emulsification solution is obtained；Wherein institute
Monomer is stated for isoprene, limonene and butyl ester, the butyl ester is isoamyl two in butyl acrylate or dibutyl itaconate, monomer
The mass ratio of alkene, limonene and butyl ester is 30~60：30：10~40；The gross mass of monomer is the 30~50% of polymerization system,
The pre-emulsification time is 0.5~2.0 hour；S2：Initiator is added into gained pre-emulsification solution, in a nitrogen atmosphere, is heated to
50~80 DEG C, 1~4MPa progress reaction 2~7 hours of pressurizeing, obtain the first reaction solution；The initiator is potassium peroxydisulfate, is drawn
Hair agent quality accounts for the 0.1~0.5% of monomer gross mass；
S3：Demulsification is carried out to the first reaction solution using calcium chloride solution and coagulates rubber, is cleaned with deionized water, is dried, obtain different
Pentadiene-limonene -ester terpolymer rubber.
2. preparation method according to claim 1, it is characterised in that also include S4 after S3：To isoprene-lemon
Alkene -ester terpolymer rubber is dissolved with solvent, obtains rubber solutions；
S5：Rubber solutions, catalyst are added sequentially in pressure reaction still, in a hydrogen atmosphere, heating compressive reaction is carried out,
Rubber is hydrogenated with, the second reaction solution is obtained；
S6：Demulsification is carried out to the second reaction solution using absolute ethyl alcohol and coagulates rubber, is then cleaned with deionized water, is dried, obtain
The isoprene of hydrogenation-limonene -ester terpolymer rubber.
3. preparation method according to claim 1 or 2, it is characterised in that in the S1；The emulsifying agent is dodecyl
Benzene sulfonic acid sodium salt or calcium dodecyl benzene sulfonate, emulsifying agent quality account for the 1~3% of monomer gross mass, and the electrolyte is potassium chloride
And/or potassium phosphate, electrolyte quality accounts for the 0.5~1.0% of monomer gross mass.
4. preparation method according to claim 3, it is characterised in that the electrolyte is potassium chloride and potassium phosphate, chlorination
Potassium quality accounts for the 0.4~0.6% of monomer gross mass, and potassium phosphate quality accounts for the 0.1~0.4% of monomer gross mass.
5. preparation method according to claim 1, it is characterised in that initiator quality accounts for monomer gross mass in the S2
0.2%.
6. preparation method according to claim 2, it is characterised in that solvent is dimethylbenzene in the S4, the rubber is molten
The mass concentration of liquid is 2~5%.
7. preparation method according to claim 2, it is characterised in that 80~150 DEG C are heated in the S5,1 is forced into
~4MPa, reacts 2~12 hours, obtains the second reaction solution.
8. preparation method according to claim 2, it is characterised in that catalyst is in rhodium, ruthenium, palladium catalyst in the S5
One kind, the addition of catalyst accounts for the 0.05~0.5% of the isoprene-limonene -ester terpolymer rubber quality.
9. product made from any described preparation method of claim 1~8.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB517302A (en) * | 1937-07-21 | 1940-01-25 | Istituto Per Lo Studio Della G | Improvements in or relating to the manufacture of synthetic rubber |
| CN1752120A (en) * | 2004-09-21 | 2006-03-29 | 上海生大企业有限公司 | Polyisoprene copolymerized omulsion and preparation of its green gloves and related products |
| CN104428348A (en) * | 2012-01-18 | 2015-03-18 | 亚克朗大学 | Terpene/isoolefin copolymers having substantially heterogeneous compositional distribution and displaying thermoplastic elastomeric properties |
| JP5748871B1 (en) * | 2014-01-21 | 2015-07-15 | 株式会社レヂテックス | Modified rubber and method for producing modified rubber |
-
2015
- 2015-09-24 CN CN201510617680.6A patent/CN105111373B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB517302A (en) * | 1937-07-21 | 1940-01-25 | Istituto Per Lo Studio Della G | Improvements in or relating to the manufacture of synthetic rubber |
| CN1752120A (en) * | 2004-09-21 | 2006-03-29 | 上海生大企业有限公司 | Polyisoprene copolymerized omulsion and preparation of its green gloves and related products |
| CN104428348A (en) * | 2012-01-18 | 2015-03-18 | 亚克朗大学 | Terpene/isoolefin copolymers having substantially heterogeneous compositional distribution and displaying thermoplastic elastomeric properties |
| JP5748871B1 (en) * | 2014-01-21 | 2015-07-15 | 株式会社レヂテックス | Modified rubber and method for producing modified rubber |
Non-Patent Citations (1)
| Title |
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| 丙烯酸酯-氯丁二烯共聚胶乳的研究—耐油制品用胶乳;朗诗清等;《特种橡胶制品》;19860401(第3期);第1-5页 * |
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