CN104693388A - Preparation method for wide temperature region damping rubber of gradual change block structure through anion method - Google Patents
Preparation method for wide temperature region damping rubber of gradual change block structure through anion method Download PDFInfo
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- CN104693388A CN104693388A CN201510150481.9A CN201510150481A CN104693388A CN 104693388 A CN104693388 A CN 104693388A CN 201510150481 A CN201510150481 A CN 201510150481A CN 104693388 A CN104693388 A CN 104693388A
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Abstract
The invention discloses a preparation method for wide temperature region damping rubber of a gradual change block structure through the anion method and belongs to the field of damping rubber preparation techniques. The method includes the following steps that firstly, solvents and monomers are uniformly stirred to be made into a reaction mixture, organic lithium initiators are added to the reaction mixture, and a polymerization reaction is triggered under the condition of 20 DEG C-130 DEG C; secondly, after the polymerization reaction is triggered 1 minute-60 minutes, modifiers are added; thirdly, after the polymerization reaction is triggered 10 minutes-160 minutes, coupling reagents are added after the modifiers are added; fourthly, terminator isopropyl alcohol is added for terminating the reaction, drying is conducted, and crude rubber is obtained; fifthly, the crud rubber is mixed to obtain mixed rubber, and the mixed rubber is vulcanized to obtain the wide temperature region damping rubber. The active anionic polymerization technology is adopted, the modifiers are added in a delayed mode, the styrene-isoprene rubber of the gradual change block structure is prepared, the damping temperature region of the rubber is widened, the defect that homopolymers and random copolymers have narrow damping temperature regions is overcome, and therefore the requirement of production practice for damping performance is met.
Description
Technical field
The present invention relates to a kind of damping rubber preparation method, be specifically related to a kind of negative ion legal system and get everything ready the method for wide temperature range damping rubber of tapered block structure.
Background technology
At present, vibration & noise is harm society, impact is produced and two large public hazards of Economic development, and adopts damping material to be one of the most effective means of vibration and noise reducing.Macromolecular material has visco-elasticity due to itself, can absorb vibration mechanical energy and acoustic energy, and changes them into heat energy and dissipate, thus reaches the object of vibration and noise reducing, becomes novel damping material.In damping polymer material, rubber plays important role.This is mainly because rubber has the following advantages: Young's modulus is little, separating vibration superior performance; Be typical viscoelastic body, have obvious hysteresis phenomenon, sound absorption vibrationproof is very effective; By different formulas and damping adjusting performance easy with other polymer complex; Also there is volume simultaneously little, lightweight, the features such as easy processing.
Macromolecular material damping depends on temperature and frequency consumingly, only just there will be maximum value in the self-energy loss of second-order transition temperature (Tg) limited proportionality.Because the Tg limited proportionality of homopolymer and random copolymers only has 20 ~ 30 DEG C, and practical application damping temperature domain is at least between 60 ~ 80 DEG C, single polymers is difficult to satisfy the demand, for widening damping temperature province, main employing physics and chemistry method realizes, as: (1) copolymerization, blended; (2) filling, plasticising etc.; (3) interpenetrating polymer networks (IPN) is prepared.Wherein chemical copolymerization method can carry out Molecular Structure Design, can meet the technical need of different field, demonstrates obvious advantage.According to group contribution analysis theories, if containing polarity, group that steric hindrance is larger in macromolecular chain, and quantity is more much more intensive, and the damping capacity of material is better.In numerous rubber, solution polymerized butadiene styrene rubber (SSBR) has wear-resisting, cold-resistant, the advantage such as heat-dissipating is low, rebound resilience is high, pressure is insensitive, easy processing, become one of main raw material preparing damping material, but common SSBR is random copolymerization type, amount of side groups is less, cause damping temperature domain narrow range, damping capacity is not high.
Summary of the invention
The present invention is directed to existing damping rubber damping temperature domain narrow range set forth above, problem that damping capacity is not high, the method for the wide temperature range damping rubber of tapered block structure and a kind of negative ion legal system of research and design is got everything ready.The technique means that the present invention adopts is as follows:
Negative ion legal system is got everything ready the method for wide temperature range damping rubber of tapered block structure, comprises the following steps:
1. solvent and monomer join in reactor, stir into homogeneous solution, add organic lithium initiator, initiated polymerization under 20-130 DEG C of condition, in described reaction mixture, the weight percent of monomer is 5-50%, and the weight percent of preferred monomers is 10-20%;
2., after initiated polymerization after 1-60 minute, add conditioning agent, the preferred joining day is 5-10 minute after initiated polymerization;
2. send out after polyreaction after 10-160 minute, add coupling agent, linked reaction 30 ~ 120 minutes, described coupling agent adds after adding conditioning agent, and the preferred joining day is 40-60 minute after initiated polymerization, 45 ~ 60 minutes preferential linked reaction time;
4. add terminator Virahol termination reaction, glue is after water vapour cohesion, and drying obtains rubber, can be dry in 110 DEG C of mills;
5. on a mill until rubber is plasticated, add vulcanizer, activator, promotor, lubricant, toughener, prepare rubber unvulcanizate, after rubber unvulcanizate sulfuration, obtain wide temperature range damping rubber;
The mol ratio of described conditioning agent and organic lithium initiator is 5.0 ~ 60.0, and preferred molar ratio is 5.0 ~ 10.0; The mol ratio of described coupling agent and organic lithium initiator is 0.1 ~ 2.0, and preferred molar ratio is 0.5 ~ 1.0.
Further, described solvent is varsol, described varsol is hexanaphthene, normal hexane, Skellysolve A, normal heptane, octane, benzene, toluene, ethylbenzene, p-Xylol, o-Xylol, m-xylene, raffinate oil in one or more, be preferably in hexanaphthene and normal hexane one or both.
Further, described monomer is monovinylarene and conjugated diene, the straight or branched alkyl-substituted styrene of described monovinylarene to be carbonatoms be 1-10, the conjugated diene of described conjugated diene to be carbonatoms be 4-12.
Further, described monovinylarene is one or more in vinylbenzene, p-methylstyrene, a vinyl toluene, 4-t-butyl styrene, alpha-methyl styrene, Vinyl toluene, is preferably vinylbenzene and/or alpha-methyl styrene; Described conjugated diene is one or more in 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-phenyl-1,3-butadiene, 1,3-pentadiene, isoprene, is preferably divinyl and/or isoprene.
Further, described organic lithium initiator be can cause described monovinylarene and conjugate diene polymerization containing lithium initiator.
Further, described organic lithium initiator is one or more in lithium methide, lithium ethide, propyl lithium, isopropyl lithium, n-Butyl Lithium, s-butyl lithium, tert-butyl lithium, amyl group lithium, hexyl lithium, cyclohexyl lithium, tertiary octyl group lithium, phenyl lithium, aminomethyl phenyl lithium, 4-butyl phenyl lithium, 2-naphthyl lithium, is preferably n-Butyl Lithium.
Further, described conditioning agent is the organic compound that can regulate described monovinylarene and conjugated diene polymer microtexture.
Further, described conditioning agent is dibutyl ether, dioxane, crown ether, R
1oCH
2cH
2oR
2, R
1oCH
2cH
2oCH
2cH
2oR
2, tetrahydrofuran (THF) (THF) or have
the substituted tetrahydrofuran of general formula, wherein: the alkyl of R to be carbonatoms be 1-10, as ethyl tetrahydrofurfuryl ether (ETE), propyl group tetrahydrofurfuryl ether; R
1and R
2for carbonatoms is the alkyl of 1-6, R
1and R
2can be identical or different, with R
1and R
2be not all good, as the ethers of symmetry, dibutyl ethylene glycol ether; Asymmetric ethers, ethylene glycol Ethyl Tertisry Butyl Ether, Ethylene Glycol Methyl tertbutyl ether.
Further, described coupling agent be can with negative ion active end group react containing multi-functional sn-containing compound.
Further, described coupling agent is one or more in tin methyltrichloride, dimethyltin chloride, tin tetrachloride, ethyl tin trichloride, ethyltin dichloride, dibutyl tin dichloride, octyl group tin trichloride, dioctyl tindichloride, tin tetrafluoride, dimethyl tin dibromide, tin tetrabromide, octyl group tribromide tin, is preferably tin tetrachloride.
Compared with the prior art, the get everything ready method of wide temperature range damping rubber of tapered block structure of a kind of negative ion legal system of the present invention adopts living anion polymerization technology, the method of conditioning agent is added by time delay, preparation has the styrene isoprene rubber of tapered block structure, widen the damping temperature domain of rubber, overcome homopolymer and the narrow shortcoming of random copolymers damping temperature domain, produce the actual requirement to damping capacity with satisfied.
Accompanying drawing explanation
Fig. 1 is the tan δ-hygrogram of embodiment of the present invention 1-6.
Fig. 2 is the tan δ-hygrogram of embodiment of the present invention 7-9.
Fig. 3 is the tan δ-hygrogram of the embodiment of the present invention 10.
Fig. 4 is the tan δ-hygrogram of embodiment of the present invention 11-16.
Fig. 5 is the tan δ-hygrogram of embodiment of the present invention 17-18.
Fig. 6 is the tan δ-hygrogram of embodiment of the present invention 19-20 and embodiment 1.
Fig. 7 is the tan δ-hygrogram of embodiment of the present invention 21-25.
In figure: X-coordinate is temperature (DEG C), ordinate zou is tan δ (mechanical loss angle tangent).
Embodiment
Embodiment 1-6
The preparation of rubber
The enforcement of polyreaction is carried out in 5 liters of stainless steel cauldrons.First add in order the conditioning agent THF of 2000g solvent hexanaphthene, 120g vinylbenzene (St), 280g isoprene (Ip) (monomer weight ratio is St/Ip=30/70) and different content respectively, the concrete add-on of THF is in table 1.Unlatching is uniformly mixed, open heating in water bath, be preheated to temperature 50 C, a certain amount of n-Butyl Lithium initiation reaction is added according to the molecular weight of design after removal of impurities, add coupling agent tin tetrachloride after polyreaction completes and carry out coupling, linked reaction adds terminator Virahol and carries out termination reaction after 1 hour, and glue is after water vapour cohesion, dry in 110 DEG C of mills, obtain SSIR rubber.
The preparation of cross-linked rubber
Carry out mixing in two rod mill according to the following formulation:
Rubber: 100phr;
Zinc oxide (activator): 3phr;
Stearic acid (lubricant): 1phr;
7# reference black (toughener): 50phr;
Sulphur (vulcanizing agent): 1.75phr;
Accelerator TBBS (promotor): 1phr;
More than 4 hours are parked after mixing, and then temperature 150 DEG C, under the above condition of pressure 100kg/cm2, sulfuration 30min, carries out performance test after sulfide film cooling.
The test of performance
Dynamic properties adopts German GABO company EPLE × OR type viscoelastic spectrometer to measure.
Specimen size: 30mm × 8mm × 1mm
Frequency: 11Hz
Temperature range :-80 DEG C ~ 100 DEG C
Intensification frequency: 3 DEG C/min.
The performance test results of cross-linked rubber prepared by embodiment 1-6 is as shown in table 1, and dynamic properties as shown in Figure 1.
Table 1
| Numbering | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 |
| THF/Li (mol ratio) | 5 | 10 | 15 | 20 | 30 | 45 |
| Shore hardness | 72 | 74 | 74 | 78 | 76 | 80 |
| 100% tensile modulus (MPa) | 3.8 | 4.6 | 4.0 | 4.4 | 3.8 | 4.6 |
| Breaking tenacity (MPa) | 17.5 | 17.2 | 17.4 | 18.7 | 16.7 | 18.4 |
| Tear strength (N/mm) | 33 | 32 | 34 | 34 | 33 | 34 |
| Elongation at break (%) | 376 | 298 | 343 | 348 | 350 | 331 |
| Tension set (%) | 10 | 10 | 11 | 10 | 12 | 11 |
| tanδ max | 0.68 | 0.85 | 0.92 | 0.97 | 1.1 | 0.99 |
From table 1, along with the increase of THF/Li mol ratio, tan δ
maxobvious increase.
As seen from Figure 1, the tan δ curve of SSIR is unimodal distribution, shows that SSIR is random structure; Along with the increase of THF/Li mol ratio, the dynamic mechanical curve of SSIR moves to high-temperature zone, and for embodiment 1, the temperature province corresponding to its effective damping value (tan δ >=0.3) is-22 ~ 16 DEG C of scopes.
Embodiment 7-9
Prepare SSIR rubber according to the method for embodiment 2, different unlike St content, concrete St content and the performance test results of cross-linked rubber as shown in table 2, dynamic properties is as shown in Figure 2.
Table 2
| Numbering | Embodiment 7 | Embodiment 8 | Embodiment 9 | Embodiment 2 |
| St(wt％) | 20.1 | 22.1 | 25.2 | 29.6 |
| Shore hardness | 68 | 70 | 68 | 74 |
| 100% tensile modulus (MPa) | 3.4 | 3.5 | 3.7 | 4.6 |
| Breaking tenacity (MPa) | 17.9 | 18.6 | 17.5 | 17.2 |
| Tear strength (N/mm) | 35 | 33 | 33 | 32 |
| Elongation at break (%) | 403 | 423 | 363 | 298 |
| Tension set (%) | 10 | 11 | 9 | 10 |
| tanδ max | 0.75 | 0.76 | 0.88 | 0.85 |
St (wt%) content in table is measured value.
From table 2, along with the increase of St content, tan δ
maxslightly increase.
As seen from Figure 2, the tan δ curve of SSIR is still unimodal distribution, shows that SSIR is random structure; Along with the increase of St content, the dynamic mechanical curve of SSIR moves to high-temperature zone, and for embodiment 7, the temperature province corresponding to effective damping value (tan δ >=0.3) is-27 ~ 12 DEG C of scopes.
Embodiment 10
SSBR rubber is prepared according to the method for embodiment 1, unlike, diolefinic monomer is 1,3-butadiene (Bd), and THF/Li mol ratio is 50.The performance test results of cross-linked rubber is as shown in table 3, and dynamic properties as shown in Figure 3.
Table 3
| Numbering | Embodiment 10 |
| Shore hardness | 68 |
| 100% tensile modulus | 3.2 |
| Breaking tenacity (MPa) | 20.9 |
| Tear strength (N/mm) | 33 |
| Tensile yield (%) | 386 |
| Tension set (%) | 10 |
| tanδ max | 0.88 |
Contrast table 1,3 visible, for SSIR under the condition of less THF add-on, tan δ
maxvalue is namely more than the tan δ of SSBR
maxvalue.Show that 3,4-Ip (isoprene) structure side base has larger volume, more effectively can increase the resistance of motion of segment, thus add intramolecular frictional force, tan δ value is obviously increased.
Embodiment 11-16
The preparation of rubber
The enforcement of polyreaction is carried out in 5 liters of stainless steel cauldrons.First 2000g hexanaphthene, 120g vinylbenzene, 360g isoprene (monomer weight ratio is St/Ip=25/75) is added in order respectively, unlatching is uniformly mixed, open heating in water bath, be preheated to temperature 50 C, a certain amount of n-Butyl Lithium initiation reaction is added according to the molecular weight of design after removal of impurities, add conditioning agent THF at different time after reaction starts, the concrete joining day, THF/Li mol ratio was 10 in table 4.Add coupling agent tin tetrachloride after polyreaction completes and carry out coupling, linked reaction adds terminator Virahol termination reaction after 1 hour, and glue is after water vapour cohesion, dry in 110 DEG C of mills, obtains SSIR rubber.
The preparation of cross-linked rubber
With embodiment 1.
Performance test
The performance test results of cross-linked rubber is as shown in table 4, and dynamic properties as shown in Figure 3.
Table 4
Compare with embodiment 1-10, from table 4, time delay adds THF and does not affect the mechanical properties.
As seen from Figure 4, along with the prolongation of THF joining day, SSIR dynamic mechanical curve presents narrow unimodal, a not obvious bimodal and obviously bimodal change, shows that structure is by the random evolution process to block structure.
Embodiment 17-18
Prepare SSIR rubber according to the method for embodiment 11, different unlike, THF joining day, the concrete joining day and the performance test results as shown in table 5, dynamic properties is as shown in Figure 5.
Table 5
| Numbering | Embodiment 17 | Embodiment 18 |
| The THF joining day (min) | 7 | 8 |
| Shore hardness | 76 | 78 |
| 100% tensile modulus (Mpa) | 3.7 | 4.0 |
| Breaking tenacity (MPa) | 17.8 | 17.7 |
| Tear strength (N/mm) | 32 | 33 |
| Elongation at break (%) | 427 | 360 |
| Tension set (%) | 13 | 12 |
| tanδ max | 0.44 | 0.32 |
As seen from Figure 5, the dynamic mechanical curve of SSIR all presents wide unimodal distribution, shows that PI-SI defines tapered block structure, does not occur obviously being separated, temperature range corresponding to effective damping value (tan δ >=0.3) ,-28 DEG C ~ 23 DEG C scopes, is obviously widened than random SSIR.
Embodiment 19-20
Prepare SSIR rubber according to the method for embodiment 11, different unlike, St content, concrete St content and the performance test results as shown in table 6, dynamic properties is as shown in Figure 6.
Table 6
Fig. 6 is visible, under time delay 5min adds THF condition, synthesized SSIR dynamic properties curve is all in wide unimodal distribution, along with the increase of St content, the dynamic mechanical curve of SSIR moves to high-temperature zone, the tan δ value of SSIR reduces, and for embodiment 10, the temperature range corresponding to its effective damping value (tan δ >=0.3) is at-28 DEG C ~ 23 DEG C.
Embodiment 21-25
Rubber SSBR is prepared according to the method for embodiment 1, unlike, diolefinic monomer is 1,3-butadiene, and THF/Li mol ratio is 10.The performance test results of cross-linked rubber is as shown in table 3, and dynamic properties as shown in Figure 7.
Table 7
As seen from Figure 7, along with the prolongation of THF joining day, the dynamic mechanical curve of synthesized SSBR sample is unimodally gradient to wider unimodal by narrow, then to presenting obvious bimodal curve, shows that structure is by the random evolution process to tapered block and two-phase block structure.Temperature range corresponding to effective damping value is obviously widened than random SSIR.
As can be seen from the above results, described block SSIR and SSBR has wide damping temperature domain, and the mechanical properties such as mechanical property breaking tenacity, elongation at break are all higher, can infer when prepared rubber is used for damping material thus, can vibration and noise reducing effectively.
The above; be only the present invention's preferably embodiment; but protection scope of the present invention is not limited thereto; anyly be familiar with those skilled in the art in the technical scope that the present invention discloses; be equal to according to technical scheme of the present invention and inventive concept thereof and replace or change, all should be encompassed within protection scope of the present invention.
Claims (10)
1. negative ion legal system is got everything ready the method for wide temperature range damping rubber for tapered block structure, it is characterized in that, comprises the following steps:
1. join in reactor by solvent and monomer, stir into homogeneous solution, add organic lithium initiator, initiated polymerization under 20-130 DEG C of condition, in described reaction mixture, the weight percent of monomer is 5-50%;
2., after initiated polymerization after 1 ~ 60 minute, conditioning agent is added;
3., after initiated polymerization after 10 ~ 160 minutes, add coupling agent, linked reaction 30 ~ 120 minutes, described coupling agent adds after adding conditioning agent;
4. add terminator Virahol termination reaction, glue is after water vapour cohesion, and drying obtains rubber;
5. on a mill until rubber is plasticated, add vulcanizer, activator, promotor, lubricant, toughener, prepare rubber unvulcanizate, after rubber unvulcanizate sulfuration, obtain wide temperature range damping rubber;
The mol ratio of described conditioning agent and organic lithium initiator is 5.0 ~ 60.0, and the mol ratio of described coupling agent and organic lithium initiator is 0.1 ~ 2.0.
2. negative ion legal system according to claim 1 is got everything ready the method for wide temperature range damping rubber of tapered block structure, it is characterized in that, described solvent is varsol, described varsol is in hexanaphthene, normal hexane, Skellysolve A, normal heptane, octane, benzene, toluene, ethylbenzene, p-Xylol, o-Xylol, m-xylene, raffinate oil one or more.
3. negative ion legal system according to claim 1 is got everything ready the method for wide temperature range damping rubber of tapered block structure, it is characterized in that, described monomer is monovinylarene and conjugated diene, described monovinylarene to be carbonatoms be 1 ~ 10 straight or branched alkyl-substituted styrene, described conjugated diene to be carbonatoms be 4 ~ 12 conjugated diene.
4. negative ion legal system according to claim 3 is got everything ready the method for wide temperature range damping rubber of tapered block structure, it is characterized in that, described monovinylarene is one or more in vinylbenzene, p-methylstyrene, a vinyl toluene, 4-t-butyl styrene, alpha-methyl styrene, Vinyl toluene; Described conjugated diene is one or more in 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-phenyl-1,3-butadiene, 1,3-pentadiene, isoprene.
5. negative ion legal system according to claim 1 is got everything ready the method for wide temperature range damping rubber of tapered block structure, it is characterized in that, described organic lithium initiator be can cause described monovinylarene and conjugate diene polymerization containing lithium initiator.
6. negative ion legal system according to claim 5 is got everything ready the method for wide temperature range damping rubber of tapered block structure, it is characterized in that, described organic lithium initiator is one or more in lithium methide, lithium ethide, propyl lithium, isopropyl lithium, n-Butyl Lithium, s-butyl lithium, tert-butyl lithium, amyl group lithium, hexyl lithium, cyclohexyl lithium, tertiary octyl group lithium, phenyl lithium, aminomethyl phenyl lithium, 4-butyl phenyl lithium, 2-naphthyl lithium.
7. negative ion legal system according to claim 1 is got everything ready the method for wide temperature range damping rubber of tapered block structure, and it is characterized in that, described conditioning agent is the organic compound that can regulate described monovinylarene and conjugated diene polymer microtexture.
8. negative ion legal system according to claim 7 is got everything ready the method for wide temperature range damping rubber of tapered block structure, and it is characterized in that, described conditioning agent is dibutyl ether, dioxane, crown ether, R
1oCH
2cH
2oR
2, R
1oCH
2cH
2oCH
2cH
2oR
2, tetrahydrofuran (THF) or have
the substituted tetrahydrofuran of general formula, the wherein alkyl of R to be carbonatoms be 1-10, R
1and R
2for carbonatoms is the alkyl of 1-6.
9. negative ion legal system according to claim 1 is got everything ready the method for wide temperature range damping rubber of tapered block structure, it is characterized in that, described coupling agent be can with negative ion active end group react containing multi-functional sn-containing compound.
10. negative ion legal system according to claim 9 is got everything ready the method for wide temperature range damping rubber of tapered block structure, it is characterized in that, described coupling agent is one or more in tin methyltrichloride, dimethyltin chloride, tin tetrachloride, ethyl tin trichloride, ethyltin dichloride, dibutyl tin dichloride, octyl group tin trichloride, dioctyl tindichloride, tin tetrafluoride, dimethyl tin dibromide, tin tetrabromide, octyl group tribromide tin.
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| CN107540890A (en) * | 2016-06-23 | 2018-01-05 | 中国石油化工股份有限公司 | Coupling agent and the conjugated diene polymer of star line blending and its preparation method and application |
| CN110128606A (en) * | 2018-02-09 | 2019-08-16 | 中国石油化工股份有限公司 | Block copolymer and block copolymer composition and vulcanized rubber and its preparation method of application and block copolymer |
| CN110128608A (en) * | 2018-02-09 | 2019-08-16 | 中国石油化工股份有限公司 | A kind of styrene-isoprene block copolymer and block copolymer composition and application |
| CN115785525A (en) * | 2021-09-10 | 2023-03-14 | 中国石油化工股份有限公司 | Structure regulator composition, liquid terpolymer and preparation method and application thereof |
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| CN110128606A (en) * | 2018-02-09 | 2019-08-16 | 中国石油化工股份有限公司 | Block copolymer and block copolymer composition and vulcanized rubber and its preparation method of application and block copolymer |
| CN110128608A (en) * | 2018-02-09 | 2019-08-16 | 中国石油化工股份有限公司 | A kind of styrene-isoprene block copolymer and block copolymer composition and application |
| CN110128606B (en) * | 2018-02-09 | 2021-07-02 | 中国石油化工股份有限公司 | Block copolymer, block copolymer composition, vulcanized rubber, application of vulcanized rubber, and preparation method of block copolymer |
| CN110128608B (en) * | 2018-02-09 | 2021-08-03 | 中国石油化工股份有限公司 | Styrene-isoprene block copolymer, block copolymer composition and application |
| CN115785525A (en) * | 2021-09-10 | 2023-03-14 | 中国石油化工股份有限公司 | Structure regulator composition, liquid terpolymer and preparation method and application thereof |
| CN115785525B (en) * | 2021-09-10 | 2024-03-26 | 中国石油化工股份有限公司 | Structure regulator composition, liquid terpolymer, preparation method and application thereof |
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