CN105985455A - Preparation method of low-odor oil-extended styrene-butadiene rubber - Google Patents
Preparation method of low-odor oil-extended styrene-butadiene rubber Download PDFInfo
- Publication number
- CN105985455A CN105985455A CN201510082106.5A CN201510082106A CN105985455A CN 105985455 A CN105985455 A CN 105985455A CN 201510082106 A CN201510082106 A CN 201510082106A CN 105985455 A CN105985455 A CN 105985455A
- Authority
- CN
- China
- Prior art keywords
- oil
- parts
- extended styrene
- weight
- low smell
- 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.)
- Granted
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 229920003048 styrene butadiene rubber Polymers 0.000 title abstract description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 66
- 229920001971 elastomer Polymers 0.000 claims abstract description 32
- 239000005060 rubber Substances 0.000 claims abstract description 32
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 25
- 239000003292 glue Substances 0.000 claims abstract description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 16
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 14
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 14
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 13
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 13
- 238000002474 experimental method Methods 0.000 claims abstract description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 7
- 239000003999 initiator Substances 0.000 claims abstract description 7
- 239000008234 soft water Substances 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 25
- 230000003750 conditioning effect Effects 0.000 claims description 23
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 10
- 239000011159 matrix material Substances 0.000 claims description 10
- 239000011591 potassium Substances 0.000 claims description 10
- 229910052700 potassium Inorganic materials 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 7
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 6
- 238000006073 displacement reaction Methods 0.000 claims description 6
- 239000003792 electrolyte Substances 0.000 claims description 6
- 239000011790 ferrous sulphate Substances 0.000 claims description 6
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 6
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 6
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 6
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 claims description 6
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 claims description 6
- JFATZQWHTPPTEJ-UHFFFAOYSA-N 6-methylheptan-3-yl 2-sulfanylpropanoate Chemical compound SC(C(=O)OC(CC)CCC(C)C)C JFATZQWHTPPTEJ-UHFFFAOYSA-N 0.000 claims description 5
- KYQLRUUOMJNTMY-UHFFFAOYSA-N N(=O)OC(C)CCCCCC.SCCC(=O)O Chemical compound N(=O)OC(C)CCCCCC.SCCC(=O)O KYQLRUUOMJNTMY-UHFFFAOYSA-N 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 238000010790 dilution Methods 0.000 claims description 4
- 239000012895 dilution Substances 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 239000000839 emulsion Substances 0.000 abstract description 10
- 239000000243 solution Substances 0.000 abstract description 8
- 239000000203 mixture Substances 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract description 3
- CFJYNSNXFXLKNS-UHFFFAOYSA-N p-menthane Chemical compound CC(C)C1CCC(C)CC1 CFJYNSNXFXLKNS-UHFFFAOYSA-N 0.000 abstract 2
- 238000009833 condensation Methods 0.000 abstract 1
- 230000005494 condensation Effects 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 229930004008 p-menthane Natural products 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 22
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 19
- 238000000034 method Methods 0.000 description 12
- 150000003254 radicals Chemical class 0.000 description 10
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 9
- 239000004816 latex Substances 0.000 description 8
- 229920000126 latex Polymers 0.000 description 8
- 238000007872 degassing Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 4
- 241001441571 Hiodontidae Species 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000007720 emulsion polymerization reaction Methods 0.000 description 4
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 210000000481 breast Anatomy 0.000 description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- SUVIGLJNEAMWEG-UHFFFAOYSA-N propane-1-thiol Chemical compound CCCS SUVIGLJNEAMWEG-UHFFFAOYSA-N 0.000 description 2
- 125000003396 thiol group Chemical class [H]S* 0.000 description 2
- 150000003573 thiols Chemical class 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-ONCXSQPRSA-N abietic acid Chemical compound C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(O)=O RSWGJHLUYNHPMX-ONCXSQPRSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- ZOJBYZNEUISWFT-UHFFFAOYSA-N allyl isothiocyanate Chemical compound C=CCN=C=S ZOJBYZNEUISWFT-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000001014 amino acid Nutrition 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002199 base oil Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 235000018417 cysteine Nutrition 0.000 description 1
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 229960001484 edetic acid Drugs 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000008164 mustard oil Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229940072033 potash Drugs 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 235000018102 proteins Nutrition 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000010092 rubber production Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010091 synthetic rubber production Methods 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
Abstract
A preparation method of low-odor oil-extended styrene-butadiene rubber comprises the following steps: (1) firstly, carrying out vacuum and nitrogen replacement on a polymerization kettle, sequentially adding soft water, an emulsifier, an electrolyte solution, a reducing agent, an environment-friendly regulator, styrene, butadiene and isoprene into the polymerization kettle, adding an initiator hydrogen peroxide to p-menthane when the temperature of the polymerization kettle is reduced to below 5 ℃, carrying out a polymerization experiment, and adding a terminator HSD to terminate the reaction when the conversion rate reaches 60% to obtain an oil-filled rubber base glue solution; (2) uniformly mixing the oil-filled gum base glue solution and the oil-filled emulsion, adding the mixture into a dilute sulfuric acid solution, stirring, controlling the temperature to be 55-65 ℃ and the time to be 5-10 minutes, and after condensation, washing and drying to obtain an oil-filled gum finished product.
Description
Technical field
The invention belongs to synthetic rubber production technical field, particularly to the oil-extended styrene buadiene rubber of a kind of low smell
Preparation method.
Background technology
Oil-extended styrene buadiene rubber has good processability, the feature that heat is low, low temperature flexibility is good, is particularly useful for
There is during tire tread glue excellent hauling ability and abrasion performance.Emulsion polymerized styrene butadiene rubber can after adding filling oil
Plasticity strengthens, is easy to mixing, rubber preparing device ability is also improved.Relative to the elastomeric market price,
The price filling oil is relatively low.Therefore, produce oil-extended styrene buadiene rubber and not only increase yield, and reduce
Production cost.
Molecular weight regulator is also called chain-transferring agent.In radical-type polymerization course of reaction, poly-in order to control
The molecular weight of compound, it is often necessary to add conditioning agent.In polymerization reaction system, conditioning agent is that a class is very alive
The material sprinkling.It is easy to react with the macromolecular radical growing, and terminates living chain, with
When conditioning agent molecule itself generate again new free radical, the activity of this free radical and macromolecular radical are lived
Property same or like, thus can continue cause polymerization.The molecule of polymer can be reduced after adding conditioning agent
Amount, does not then have too much influence to polymerization rate.In addition, the radical-type polymerization for alkadienes is anti-
For answering process, add conditioning agent, in addition to can controlling molecular weight, polymer molecule can also be reduced
On chain 1,2 structures or 1,3 structures, so also just decrease polydiene and occur branched, crosslinked and produce
The hidden danger of gel.
Most emulsion polymerizations belong to free radical type reaction.Owing to macromolecular radical is closed in that
In this isolated emulsion particle, (or molecular weight is extremely low only to be expanded to initial radical in emulsion particle by aqueous phase
Living chain), there is to terminate reaction in free radical chain that could be original with emulsion particle, and in different emulsion particle
Free radical then have no chance to collide each other and the possibility of chain termination reaction occurs.Therefore with other freely
Fundamental mode polymerization process is compared, and emulsion polymerization chain termination speed is low, and the life-span of macromolecular radical is long,
The sufficient time can be had to carry out chain growth, and the molecular weight of the polymer therefore being prepared by emulsion method is than other
Polymerization is much bigger.Meanwhile, the polymerisation carrying out in emulsion particle is mostly atactic polymerization, therefore with breast
The polymer that liquid method obtains easily contains more 1,2 structures or 1,3 structures.Therefore conditioning agent is added to control
The molecular weight of polymer processed and molecular structure just seem more important, for breast for emulsion polymerization process
Poly-butadiene-styrene rubber is all the more so for producing.
Many sulfur-bearings, nitrogen, phosphorus, selenium and have the compound of unsaturated bond all can conduct in emulsion polymerisation system
Conditioning agent.For the emulsion polymerization process of many monomers, most conditioning agents is applied to be mercaptan, wherein
Including positive mercaptan and branched mercaptan, and mercaptan primary, secondary, tertiary all can be applied.Research discovery, uses
The carbon number making adjustments in the thiol molecule of agent is generally 5-14.In organic chemistry, mercaptan is to comprise mercapto
One class non-aromatic component of base functional group (-SH).The oxygen can regarded as in alcohol is replaced by sulphur, sulfhydryl
Or the organic compound that sulfydryl SH is connected with aliphatic group.Sulfydryl be connected to form containing phenol organic matter
Compound claims thiophenol.It is present in base oil, be usually with the various mercaptan based on ethyl mercaptan.Additionally, alkene
Propanethiol is present in mustard oil, and amino acid, cysteine containing sulfydryl are present in protein.Sulphur
Alcohol, thiophenol character similar to alcohol, phenol.Mercaptan and thiophenol have strong stink, and ethyl mercaptan is in atmosphere
Concentration reach 50,000,000,000/for the moment, can smell an offensive odor.
The molecular weight regulator that current oil-filled emulsion polymerized styrene butadiene rubber production technology uses is tert-dodecyl mercaptan.Fourth
The on-the-spot thiol smell of benzene rubber Workshop Production is dense, unpleasant, and mercaptan is also toxic, operator
Member's work under bad environment.Use novel molecular amount conditioning agent to replace mercaptan, the stink of mercaptan can be avoided, this
For realize environmental protection, cleaning produce all have very important significance.
Content of the invention
It is an object of the invention to provide a kind of novel tasteless molecular weight regulator and replace mercaptan, both permissible
Avoid the stink of mercaptan, the effect same with tert-dodecyl mercaptan during polymerisation, can be reached again, this for
Realize that environmental protection, cleaning produce and all have very important significance.
The present invention provides the oil-extended styrene buadiene rubber preparation method of a kind of low smell, comprises the steps:
(1) vacuum, nitrogen displacement are first carried out to polymeric kettle, successively by soft water, emulsifying agent, electrolyte
Solution, reducing agent, environment-friendly type conditioning agent, styrene, butadiene, isoprene join in polymeric kettle,
When polymeric kettle temperature is down to below 5 DEG C, adds initiator hydrogen peroxide to alkane in the Meng, carry out polymerization experiment,
When conversion ratio reaches 60%, add terminator HSD to terminate reaction, obtain oil-filled matrix plinth glue；
(2) oil-filled matrix plinth glue is mixed with filling fat liquor, joins in dilution heat of sulfuric acid,
Stirring, temperature controls at 55 DEG C～65 DEG C, and the time is 5～10 minutes, and after cohesion, washing is dried, and obtains
Oil-filled glue finished product.
The method have the benefit that
When oil-extended styrene buadiene rubber prepared by novel molecular amount conditioning agent of the present invention, whether polymerization stage,
Deaeration stage, blending stage, cohesion washing stage, all there is no obvious peculiar smell, it is achieved that environmental protection produces,
Reduce the infringement to operating personnel.
Detailed description of the invention
Hereinafter embodiments of the invention are elaborated: the present embodiment is premised on technical solution of the present invention
Under implement, give detailed embodiment and process, but protection scope of the present invention be not limited to following
Embodiment, the experimental technique of unreceipted actual conditions in the following example, generally according to normal condition.
The oil-extended styrene buadiene rubber preparation method of low smell of the present invention, wherein, step (1) comprises
Polymeric component and parts by weight are preferably:
The oil-extended styrene buadiene rubber preparation method of low smell of the present invention, wherein, emulsifying agent is disproportionated rosin
Acid potash soap, its parts by weight preferably 4.5 parts.
The oil-extended styrene buadiene rubber preparation method of low smell of the present invention, wherein, component that electrolyte comprises
And parts by weight are preferably: phosphoric acid 0.2～0.3 part, 0.3～0.5 part of potassium hydroxide, ethylenediamine tetra-acetic acid four
Sodium salt 0.03 part, neopelex 0.1～0.2 part.
The oil-extended styrene buadiene rubber preparation method of low smell of the present invention, wherein, component that reducing agent comprises
And parts by weight are preferably: 0.01 part of ferrous sulfate, rongalite 0.03～0.05 part, second two
Amine tetraacethyl tetrasodium salt 0.025 part.
The oil-extended styrene buadiene rubber preparation method of low smell of the present invention, wherein, environment-friendly type conditioning agent comprises
Component and parts by weight be preferably: 3-isooctyl mercaptopropionate 0.05～0.10 part, 3-mercaptopropionic acid-2-
Octyl Nitrite 0.05～0.10 part.
The oil-extended styrene buadiene rubber preparation method of low smell of the present invention, wherein, fills what fat liquor comprised
Component and parts by weight are preferably: PUR softening oil No. 3 21.5～23.5 parts, water
11.7～12.0 parts, isproportionated potassium rosinate 2.8～3.0 parts.
The oil-extended styrene buadiene rubber preparation method of low smell of the present invention, wherein, dilute sulphur in step (2)
Acid solution pH value is preferably 3～4.
Embodiment 1:
(1) first carry out vacuum, nitrogen displacement to polymeric kettle.Successively by soft water, emulsifying agent, electrolyte
Solution, reducing agent, environment-friendly type conditioning agent, styrene, butadiene, isoprene join in polymeric kettle,
When polymeric kettle temperature is down to 5 DEG C, add initiator hydrogen peroxide to alkane in the Meng, carry out polymerization experiment, when turn
When rate reaches 60%, add terminator HSD to terminate reaction, obtain oil-filled matrix plinth glue.
(2) by oil-filled matrix plinth glue with fill fat liquor mix, join pH value be 3 dilute
In sulfuric acid solution, stirring, temperature controls at 55 DEG C, and the time is 5 minutes, and after cohesion, washing is dried,
Obtain oil-filled glue finished product.
Polymeric component and parts by weight that above-mentioned steps (1) comprises are:
Mentioned emulsifier is included as isproportionated potassium rosinate, and its parts by weight are 3.5 parts.
Component and number that above-mentioned electrolyte comprises be:
Component and number that above-mentioned reducing agent comprises be:
0.01 part of ferrous sulfate
Rongalite 0.03 part
Tetrasodium salt of EDTA 0.025 part
Component and number that above-mentioned environment-friendly type conditioning agent comprises be:
3-isooctyl mercaptopropionate 0.05 part
3-mercaptopropionic acid-2-Octyl Nitrite 0.05 part
Component and parts by weight that described filling fat liquor comprises are:
PUR softening oil No. 3 21.5 parts
11.7 parts of water
Isproportionated potassium rosinate 2.8 parts
There is no pungent mercaptan taste in polymerization process, in latex degasification process.Rubber sample Mooney point is 54.
Embodiment 2:
(1) first carry out vacuum, nitrogen displacement to polymeric kettle.Successively by soft water, emulsifying agent, electrolyte
Solution, reducing agent, environment-friendly type conditioning agent, styrene, butadiene, isoprene join in polymeric kettle,
When polymeric kettle temperature is down to 5 DEG C, add initiator hydrogen peroxide to alkane in the Meng, carry out polymerization experiment, when turn
When rate reaches 60%, add terminator HSD to terminate reaction, obtain oil-filled matrix plinth glue.
(2) by oil-filled matrix plinth glue with fill fat liquor mix, join pH value be 4 dilute
In sulfuric acid solution, stirring, temperature controls at 65 DEG C, and the time is 10 minutes, and after cohesion, washing is dried,
Obtain oil-filled glue finished product.
Polymeric component and parts by weight that above-mentioned steps (1) comprises are:
Mentioned emulsifier is included as isproportionated potassium rosinate, and its parts by weight are 5.0 parts.
Component and number that above-mentioned electrolyte comprises be:
Component and number that above-mentioned reducing agent comprises be:
0.01 part of ferrous sulfate
Rongalite 0.05 part
Tetrasodium salt of EDTA 0.025 part
Component and number that above-mentioned environment-friendly type conditioning agent comprises be:
3-isooctyl mercaptopropionate 0.1 part
3-mercaptopropionic acid-2-Octyl Nitrite 0.1 part
Component and parts by weight that described filling fat liquor comprises are:
PUR softening oil No. 3 23.5 parts
12.0 parts of water
Isproportionated potassium rosinate 3.0 parts
There is no pungent mercaptan taste in polymerization process, in latex degasification process.Rubber sample Mooney point is 44.
Embodiment 3:
(1) first carry out vacuum, nitrogen displacement to polymeric kettle.Successively by soft water, emulsifying agent, electrolyte
Solution, reducing agent, environment-friendly type conditioning agent, styrene, butadiene, isoprene join in polymeric kettle,
When polymeric kettle temperature is down to 5 DEG C, add initiator hydrogen peroxide to alkane in the Meng, carry out polymerization experiment, when turn
When rate reaches 60%, add terminator HSD to terminate reaction, obtain oil-filled matrix plinth glue.
(2) by oil-filled matrix plinth glue with fill fat liquor mix, join pH value be 3.5 dilute
In sulfuric acid solution, stirring, temperature controls at 60 DEG C, and the time is 7.5 minutes, and after cohesion, washing is dried,
Obtain oil-filled glue finished product.
Polymeric component and parts by weight that above-mentioned steps (1) comprises are:
Mentioned emulsifier is included as isproportionated potassium rosinate, and its parts by weight are 4.2 parts.
Component and number that above-mentioned electrolyte comprises be:
Component and number that above-mentioned reducing agent comprises be:
0.01 part of ferrous sulfate
Rongalite 0.04 part
Tetrasodium salt of EDTA 0.025 part
Component and number that above-mentioned environment-friendly type conditioning agent comprises be:
3-isooctyl mercaptopropionate 0.07 part
3-mercaptopropionic acid-2-Octyl Nitrite 0.08 part
Component and parts by weight that described filling fat liquor comprises are:
PUR softening oil No. 3 22.5 parts
11.9 parts of water
Isproportionated potassium rosinate 2.9 parts
There is no pungent mercaptan taste in polymerization process, in latex degasification process.Rubber sample Mooney point is 49.
Comparative example:
(1) first carry out vacuum, nitrogen displacement to polymeric kettle.Successively by soft water, emulsifying agent, electrolyte
Solution, reducing agent, tert-dodecyl mercaptan, styrene, butadiene, isoprene join in polymeric kettle,
When polymeric kettle temperature is down to 5 DEG C, add initiator hydrogen peroxide to alkane in the Meng, carry out polymerization experiment, when turn
When rate reaches 60%, add terminator HSD to terminate reaction, obtain oil-extended styrene buadiene rubber base latex；
(2) oil-extended styrene buadiene rubber base latex and age resistor emulsion are blended uniformly, add concentration to be 0.5%
Dilution heat of sulfuric acid in, stirring, temperature controls at 60 DEG C, and the time is 5 minutes, and after cohesion, washing is dry
Dry, obtain oil-filled glue finished product.
Polymeric component and parts by weight that above-mentioned steps (1) comprises are:
Described emulsifying agent is isproportionated potassium rosinate, and its parts by weight are 4.5 parts.
Component and parts by weight that described electrolyte comprises are:
Component and parts by weight that described reducing agent comprises are:
0.01 part of ferrous sulfate
Rongalite 0.03 part
Tetrasodium salt of EDTA 0.025 part
Polymerization process has pungent mercaptan taste, latex degasification process also has pungent mercaptan taste.Oil-filled glue
Sample Mooney point is 51.
Contrast three embodiments and comparative example, first see the oil-filled glue sample gate of three embodiments and comparative example
Buddhist nun's viscosity, all between 44～54, all controls in oil-extended styrene buadiene rubber top grade product indication range, this explanation
The low smell environment-friendly type conditioning agent that the present invention uses serves common butadiene-styrene rubber conditioning agent tert-dodecyl mercaptan
Effect, may be used for synthesizing oil-extended styrene buadiene rubber.
Secondly, in three embodiment polymerizations and latex degasification process, the mercaptan taste not all being pungent, and
In comparative example polymerization and latex degasification process, all there is the mercaptan taste being pungent especially, make us very uncomfortable, say
The low smell environment-friendly type conditioning agent that the bright present invention uses decreases in oil-extended styrene buadiene rubber preparation process really
Pungent undesirable smell.
Claims (8)
1. an oil-extended styrene buadiene rubber preparation method for low smell, comprises the steps:
(1) vacuum, nitrogen displacement are first carried out to polymeric kettle, successively by soft water, emulsifying agent, electrolyte
Solution, reducing agent, environment-friendly type conditioning agent, styrene, butadiene, isoprene join in polymeric kettle,
When polymeric kettle temperature is down to below 5 DEG C, adds initiator hydrogen peroxide to alkane in the Meng, carry out polymerization experiment,
When conversion ratio reaches 60%, add terminator HSD to terminate reaction, obtain oil-filled matrix plinth glue；
(2) oil-filled matrix plinth glue is mixed with filling fat liquor, joins in dilution heat of sulfuric acid,
Stirring, temperature controls at 55 DEG C～65 DEG C, and the time is 5～10 minutes, and after cohesion, washing is dried, and obtains
Oil-filled glue finished product.
2. the oil-extended styrene buadiene rubber preparation method of low smell according to claim 1, it is characterised in that:
Polymeric component and parts by weight that step (1) comprises are:
3. the oil-extended styrene buadiene rubber preparation method of low smell according to claim 1, it is characterised in that:
Emulsifying agent is isproportionated potassium rosinate, and its parts by weight are 3.5～5.0 parts.
4. the oil-extended styrene buadiene rubber preparation method of low smell according to claim 1, it is characterised in that:
Component and parts by weight that described electrolyte comprises are: phosphoric acid 0.2～0.3 part, 0.3～0.5 part of potassium hydroxide,
Tetrasodium salt of EDTA 0.03 part, neopelex 0.1～0.2 part.
5. the oil-extended styrene buadiene rubber preparation method of low smell according to claim 1, it is characterised in that:
Component and parts by weight that described reducing agent comprises are: 0.01 part of ferrous sulfate, rongalite
0.03～0.05 part, tetrasodium salt of EDTA 0.025 part.
6. the oil-extended styrene buadiene rubber preparation method of low smell according to claim 1, it is characterised in that:
Component and parts by weight that described environment-friendly type conditioning agent comprises are: 3-isooctyl mercaptopropionate 0.05～0.10 part,
3-mercaptopropionic acid-2-Octyl Nitrite 0.05～0.10 part.
7. the oil-extended styrene buadiene rubber preparation method of low smell according to claim 1, it is characterised in that:
Fill the component that comprises of fat liquor and parts by weight are: PUR softening oil No. 3 21.5～23.5 parts, water
11.7～12.0 parts, isproportionated potassium rosinate 2.8～3.0 parts.
8. the oil-extended styrene buadiene rubber preparation method of low smell according to claim 1, it is characterised in that:
In step (2), dilution heat of sulfuric acid pH value is 3～4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510082106.5A CN105985455B (en) | 2015-02-15 | Preparation method of low-odor oil-extended styrene-butadiene rubber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510082106.5A CN105985455B (en) | 2015-02-15 | Preparation method of low-odor oil-extended styrene-butadiene rubber |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105985455A true CN105985455A (en) | 2016-10-05 |
| CN105985455B CN105985455B (en) | 2018-06-01 |
Family
ID=
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107312125A (en) * | 2017-07-14 | 2017-11-03 | 合肥市远程胶塑有限公司 | A kind of modified oil-extended styrene buadiene rubber formula and its preparation technology |
| CN107602765A (en) * | 2017-09-26 | 2018-01-19 | 青岛瑞林材料科技有限公司 | A kind of preparation method of oil-filled polydiene rubber |
| CN108203523A (en) * | 2016-12-20 | 2018-06-26 | 中国石油天然气股份有限公司 | Preparation method of oil-extended styrene-butadiene rubber |
| CN108203486A (en) * | 2016-12-20 | 2018-06-26 | 中国石油天然气股份有限公司 | Preparation method of environment-friendly oil-extended styrene-butadiene rubber |
| CN108467523A (en) * | 2018-03-09 | 2018-08-31 | 杨春花 | A kind of high-elasticity thermoplastic resin combination and preparation method thereof |
| CN109776726A (en) * | 2017-11-15 | 2019-05-21 | 中国石油天然气股份有限公司 | Preparation method of styrene butadiene rubber and styrene butadiene rubber |
| CN114805686A (en) * | 2021-01-19 | 2022-07-29 | 中国石油天然气股份有限公司 | Oil-extended styrene-butadiene rubber and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020034703A1 (en) * | 2000-07-19 | 2002-03-21 | Hiroshi Yamazaki | Toner for developing electrostatic latent image |
| CN101463110A (en) * | 2008-12-31 | 2009-06-24 | 大连理工大学 | Emulsion polymerized styrene-isoprene-butadiene terpolymer and preparation thereof |
| CN102325799A (en) * | 2009-02-19 | 2012-01-18 | 巴斯夫欧洲公司 | Aqueous polymer dispersion made of vinylaromatic compound, conjugated aliphatic diene, and ethylenically unsaturated acid |
| CN102585095A (en) * | 2012-03-16 | 2012-07-18 | 北京化工大学 | Preparation method of emulsion-polymerized styrene butadiene rubber |
| CN102731723A (en) * | 2011-04-13 | 2012-10-17 | 住友橡胶工业株式会社 | Diene polymer and production method thereof |
| CN103113525A (en) * | 2013-01-23 | 2013-05-22 | 华东理工大学 | Preparation method of low-odor polymer emulsion |
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020034703A1 (en) * | 2000-07-19 | 2002-03-21 | Hiroshi Yamazaki | Toner for developing electrostatic latent image |
| CN101463110A (en) * | 2008-12-31 | 2009-06-24 | 大连理工大学 | Emulsion polymerized styrene-isoprene-butadiene terpolymer and preparation thereof |
| CN102325799A (en) * | 2009-02-19 | 2012-01-18 | 巴斯夫欧洲公司 | Aqueous polymer dispersion made of vinylaromatic compound, conjugated aliphatic diene, and ethylenically unsaturated acid |
| CN102731723A (en) * | 2011-04-13 | 2012-10-17 | 住友橡胶工业株式会社 | Diene polymer and production method thereof |
| CN102585095A (en) * | 2012-03-16 | 2012-07-18 | 北京化工大学 | Preparation method of emulsion-polymerized styrene butadiene rubber |
| CN103113525A (en) * | 2013-01-23 | 2013-05-22 | 华东理工大学 | Preparation method of low-odor polymer emulsion |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108203523A (en) * | 2016-12-20 | 2018-06-26 | 中国石油天然气股份有限公司 | Preparation method of oil-extended styrene-butadiene rubber |
| CN108203486A (en) * | 2016-12-20 | 2018-06-26 | 中国石油天然气股份有限公司 | Preparation method of environment-friendly oil-extended styrene-butadiene rubber |
| CN108203523B (en) * | 2016-12-20 | 2020-04-10 | 中国石油天然气股份有限公司 | Preparation method of oil-extended styrene-butadiene rubber |
| CN107312125A (en) * | 2017-07-14 | 2017-11-03 | 合肥市远程胶塑有限公司 | A kind of modified oil-extended styrene buadiene rubber formula and its preparation technology |
| CN107602765A (en) * | 2017-09-26 | 2018-01-19 | 青岛瑞林材料科技有限公司 | A kind of preparation method of oil-filled polydiene rubber |
| CN107602765B (en) * | 2017-09-26 | 2019-11-22 | 青岛瑞林材料科技有限公司 | A kind of preparation method of oil-filled polydiene rubber |
| CN109776726A (en) * | 2017-11-15 | 2019-05-21 | 中国石油天然气股份有限公司 | Preparation method of styrene butadiene rubber and styrene butadiene rubber |
| CN109776726B (en) * | 2017-11-15 | 2021-11-02 | 中国石油天然气股份有限公司 | Preparation method of styrene butadiene rubber and styrene butadiene rubber |
| CN108467523A (en) * | 2018-03-09 | 2018-08-31 | 杨春花 | A kind of high-elasticity thermoplastic resin combination and preparation method thereof |
| CN114805686A (en) * | 2021-01-19 | 2022-07-29 | 中国石油天然气股份有限公司 | Oil-extended styrene-butadiene rubber and preparation method thereof |
| CN114805686B (en) * | 2021-01-19 | 2024-03-01 | 中国石油天然气股份有限公司 | Oil-extended styrene butadiene rubber and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| AU646215B2 (en) | Polymers derived from a conjugated diolefin, a vinyl- substituted aromatic compound, and olefinically unsaturated nitrile | |
| CN104945817B (en) | A kind of itaconate/butadiene copolymer type biological engineering rubber and preparation method thereof | |
| CN106459484B (en) | Stabilized rubber | |
| JP2000256513A (en) | Rubber compound containing solution rubber having carboxyl group | |
| JP5658169B2 (en) | Method for increasing monomer conversion in emulsion polymerization. | |
| CN109776726A (en) | Preparation method of styrene butadiene rubber and styrene butadiene rubber | |
| CN105837752A (en) | Preparation method of cold-resistant nitrile rubber | |
| CN105732914B (en) | Preparation method of lignin-xanthan gum modified powder butadiene-acrylonitrile polymer | |
| CN105985455A (en) | Preparation method of low-odor oil-extended styrene-butadiene rubber | |
| CN106554463B (en) | A kind of modified styrene-butadiene latex of the emulsified asphalt of high-solid lower-viscosity and preparation method thereof | |
| CN105985455B (en) | Preparation method of low-odor oil-extended styrene-butadiene rubber | |
| CN1300800A (en) | Solution poly merized rubber having non-polar side group | |
| CN105778189A (en) | Oil-extended oxygenated graphene binary emulsion coprecipitated rubber and preparation method thereof | |
| CN106132998A (en) | Polychloroprene latex, polychloroprene latex compositions and dip mold body | |
| CN108203486A (en) | Preparation method of environment-friendly oil-extended styrene-butadiene rubber | |
| CN108570121A (en) | A kind of preparation method of the polymer support of pre-dispersed rubber chemicals | |
| CN108203523A (en) | Preparation method of oil-extended styrene-butadiene rubber | |
| TWI815458B (en) | A method for preparing latex composition for dip-forming | |
| CN103539948B (en) | Preparation method of high-strength adhesive powder chloroprene rubber | |
| JP5228333B2 (en) | Chloroprene-based copolymer latex, production method thereof and use thereof | |
| TW201609983A (en) | Method for producing rubber composition, rubber composition, compound, and method for improving silica yield rate of rubber composition | |
| CN115304711A (en) | Modified emulsion polymerized styrene-butadiene rubber latex, modified emulsion polymerized styrene-butadiene rubber and preparation method of modified emulsion polymerized styrene-butadiene rubber latex and modified emulsion polymerized styrene-butadiene rubber | |
| CN111560096B (en) | Preparation method of styrene butadiene rubber | |
| CN110184001A (en) | Anti- guide-lighting adhesive of one kind and preparation method thereof | |
| CN106699971A (en) | Environment-friendly carboxylic butadiene-styrene latex for papermaking and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |