CN109337012A - A kind of preparation method of phenol modified copolymer Petropols - Google Patents

A kind of preparation method of phenol modified copolymer Petropols Download PDF

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Publication number
CN109337012A
CN109337012A CN201811014230.8A CN201811014230A CN109337012A CN 109337012 A CN109337012 A CN 109337012A CN 201811014230 A CN201811014230 A CN 201811014230A CN 109337012 A CN109337012 A CN 109337012A
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modified copolymer
preparation
phenol modified
phenol
copolymer petropols
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CN109337012B (en
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王斌
孙向东
贾立朋
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Henghe Materials and Science Technology Co Ltd
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Henghe Materials and Science Technology Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00Chemical modification by after-treatment
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00Polymerisation catalysts
    • C08F4/06Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen
    • C08F4/12Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen of boron, aluminium, gallium, indium, thallium or rare earths
    • C08F4/14Boron halides or aluminium halides; Complexes thereof with organic compounds containing oxygen

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)

Abstract

The present invention relates to a kind of preparation methods of phenol modified copolymer Petropols, it include: to obtain polymer raw B after C10 fraction A is mixed with phenolic monomers and C5~C10 monoolefine, solvent is first added in the reaction kettle with stirring, then polymer raw and Friedel-Crafts catalyst are added simultaneously, reaction obtains polymer fluid, post-treated to obtain phenol modified copolymer Petropols.Modified copolymer Petropols of the invention are of light color, the amount of dissolution is low, have stronger polymer polarity, good with the compatibilities such as ink, NBR rubber, CR rubber, are highly suitable to be applied for the fields such as compounding rubber, colored printing.

Description

A kind of preparation method of phenol modified copolymer Petropols
Technical field
The invention belongs to Petropols field, in particular to a kind of preparation method of phenol modified copolymer Petropols.
Background technique
Petropols are with by-product C5, C9 fraction of ethylene unit etc. for primary raw material, through catalytic polymerization or free radical It polymerize low average molecular weight polymers in obtained solid-state or viscous liquid.By resin constitute monomer and molecular structure, Aromatic Petroleum Resins, aliphatic petroleum resin and alicyclic petroleum resin etc. can be roughly divided into.
Ethylene by-product C10 fraction, that is, C10 raffinates oil, and obtains after extracting naphthalene for cracking naphthalene fraction, wherein containing indenes (Indene), methyl indenes (Methyl-Indene), methyl styrene (Methyl-Styrene), naphthalene, methyl naphthalene etc. are suitable for closing At aromatic monomer, these aromatic monomers all contain big conjugated electrons cloud structure, be easy with it is certain possess electrophilic group monomer into Row copolymerization;Furthermore aromatic ring is also an ideal electrophilic substitution reaction substrate, and all kinds of polar groups are easily introduced on aromatic ring It learns and is modified.
Petropols pertain generally to low pole resin, and wherein the polarity of Aromatic Petroleum Resins is than aliphatic and alicyclic resin It is slightly strong.Existing part research enhances Petropols polarity by introducing the modes such as acid anhydrides, such as JP1987212411, JP1992063822, JP1998195189 etc. access carboxylic acid group in molecular resin end group, improve compatibility or oil resistivity etc., Make it suitable for the fields such as ink printing, coating, electronics.US4603186 provides a kind of acrylonitrile-metering system of low inherent viscosity Sour methyl esters-methyl styrene/styrene-indenes quadripolymer preparation method is prepared with highly polar water solubility tree Rouge.CN101649579 discloses one kind with styrene, acrylic ester monomer, cationic monomer etc. for copolymeric material, through maleic acid Acid anhydride (MAH) is modified, the method for preparing cation high molecular base petroleum resin neutral sizing agent.US5457175 discloses a kind of low soft The terpene-pheiiol resins for changing point, can be used for adhesive and ink area.
How Petropols polarity is improved to improve and ink pigment, polar rubber such as nitrile rubber NBR, neoprene CR Deng compatibility, improve oil resistivity, wearability etc. be always industry difficult point, limit resin in high-grade modified rubber, printing The application in equal fields;Meanwhile colored ink, rubber inner tube glue etc. also require Petropols to have extremely shallow color number and extremely low wave Hair point.
Summary of the invention
Technical problem to be solved by the invention is to provide a kind of preparation method of phenol modified copolymer Petropols, this method The modified copolymer Petropols being prepared are of light color, the amount of dissolution is low, have stronger polymer polarity, with ink, NBR rubber The compatibilities such as glue, CR rubber are good, are highly suitable to be applied for the fields such as compounding rubber, colored printing.
The present invention provides a kind of preparation methods of phenol modified copolymer Petropols, comprising:
(1) the C10 fraction A by Crude products.deep process C10 raw material rectification under vacuum interception boiling point at 160~210 DEG C, with phenols list Body and C5~C10 monoolefine 1:(0.01~0.3 in mass ratio): (0~0.5) is mixed to get polymer raw B;
(2) solvent of total 30~60wt% of material is first added in the reaction kettle with stirring, it is former that polymerization is then added simultaneously Expect B and Friedel-Crafts catalyst, after reacting 1.5~3h at -20~30 DEG C, is warming up to 30~55 DEG C of insulation reactions 1 ~3h, obtains polymer fluid;
(3) it by polymer fluid alkali cleaning, is washed out to neutrality, obtains resin liquid (milky to light yellow);Then by resin Liquid rectification under vacuum is to get phenol modified copolymer Petropols.
The component of C10 fraction A in the step (1) includes: 5~25wt% of methyl styrene, 5~50wt% of indenes, first Base 5~50wt% of indenes, 0~2wt% of dicyclopentadiene, remaining is the saturation aromatic component of C8~C10.
Phenolic monomers in the step (1) are phenol, cresols, hydroquinone, p-tert-butylphenol PTBP, 2- tert-butyl One or more of cresols, benzenetriol.
C5~C10 monoolefine in the step (1) is iso-amylene, cyclopentene, 1- amylene, vinylcyclohexene VCH, α- One of firpene, nopinene, limonene.
Solvent in the step (2) is one of tetrahydroindene, indane, hexahydro indane, naphthane, or is existed for boiling point 80~200 DEG C of saturation aromatic hydrocarbons mixture, such as benzene,toluene,xylene, trimethylbenzene.
Friedel-Crafts catalyst in the step (2) is gas boron trifluoride, in boron trifluoride complex It is a kind of;Catalyst charge is 0.1~3wt% of total material.
The boron trifluoride complex is boron trifluoride ether or boron trifluoride butyl oxide.
Alkali cleaning in the step (3) is specially to use the alkali cleaning at 30~90 DEG C of 5wt%NaOH aqueous solution.
The technological parameter of rectification under vacuum in the step (3) are as follows: pressure -0.085~-0.095MPa, temperature 240~ 300℃。
The softening point of phenol modified copolymer Petropols in the step (3) is 80~130 DEG C, Gardner color number≤6#, Hydroxyl equivalent (ME) it is 200~8000g/eq, volatile matter≤2.0wt%.
Polymer can be divided into polar polymer and non-polar polymer, but the classification method of this polymer it is relatively more general and And it is not easy to define;Usual non-polar polymer refers to the polymer that dipole moment is zero, corresponding dipole moment > 0Cm's For polar polymer.The Petropols that traditional handicraft is prepared are low pole polymer, by similar compatibility principle, with pole Property rubber and printing ink compatibility it is poor, therefore the present invention provides a kind of methods for preparing highly polar Petropols.It is poly- Solubility parameter acquisition can be measured by dipole moment theoretical calculation or solwution method by closing object polarity, and method is complex, unfavorable It is used in experiment and production;Therefore pass through the hydroxyl equivalent (M of measurement modified petroleum resin in the present inventionE) indicate its polarity, MEValue is got over The big polarity for indicating phase emergencing copolymer is weaker.
The amount of dissolution of rubber sheet gasket is the small molecule object in an important indicator, with resin for evaluate adhesiveness increasing and modifying resin Matter content is closely related, differentiates its dissolving out capability superiority and inferiority by the volatile matter under measurement modified petroleum resin high temperature in the present invention.
Beneficial effect
(1) present invention is reacted using C10 component, phenolic monomers, monoolefine through Friedel-Crafts catalyst To with larger polar modified copolymer Petropols, possess fabulous compatibility with polar rubber, ink etc.;
(2) by adjusting modified monomer in raw material and C10 can poly group divide ratio, can be adjusted according to the needs the softening of resin Point, color number, hydroxyl equivalent MEEtc. performances, so that it is possessed extensive use field;
(3) present invention process is easy, and the modified copolymer Petropols of preparation have low-down volatile matter, possesses outstanding The anti-dissolving out capability of rubber, is highly suitable to be applied for the fields such as compounding rubber, colored printing.
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, those skilled in the art Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited Range.
Ethylene by-product C10 raw material described in embodiment and the typical composition of the C10 fraction A obtained through rectification under vacuum are as follows:
The typical composition of C10 raw material and fraction A, wt%
Component C10 raw material C10 fraction A
Styrene 2.5 0.1
Dimethylbenzene 3.0 2.0
Methyl styrene 13.0 18.0
Trimethylbenzene 7.0 15.0
Dicyclopentadiene 0.5 1.0
Indenes 16.0 28.0
Methyl indenes 18.0 35.0
Naphthalene 11.0 0.1
Remaining component 29.0 0.8
Examples 1 to 6
Using C10 fraction A, p-tert-butylphenol PTBP, iso-amylene as raw material, indane is solvent, gas BF3For catalyst system Standby phenol modified petroleum resin, wherein solvent accounts for the 50wt% of total quality of material, and catalyst amount is total quality of material 0.3wt%.
Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5 Embodiment 6
C10 fraction A ratio 1 1 1 1 1 1
PTBP ratio 0.05 0.05 0.1 0.1 0.2 0.2
Iso-amylene ratio 0 0.25 0.25 0.5 0.25 0.5
Yield, wt% 38.2 35.5 35.0 33.3 32.0 31.6
Softening point, DEG C 122.0 115.0 104.5 90.5 94.0 87.5
Color number, # 3 2 4 4 6 5
ME, g/eq 5715.47 5880.24 2721.30 2625.02 1043.59 1102.44
* -10 DEG C of reaction temperature, reaction time 2h, 45 DEG C of holding temperature, soaking time 2h;Resin liquid is pressed in -0.085MPa Under power, temperature is 280 DEG C of rectifications under vacuum.
As seen from the above table, in modified petroleum resin polymer raw proportion, as PTBP content increases, the softening point of resin It reduces, hydroxyl equivalent MEIt is gradually reduced, the enhancing of resin polarity, but color of resin deepens.Iso-amylene content increases in ingredient, can be with Resin softening point and color number are reduced, but to MEIt influences little.
Embodiment 7
C10 fraction A, phenol and vinylcyclohexene VCH 1:0.15:0.5 in mass ratio are mixed to get polymer raw B, The mixed xylenes solvent of total quality of material 40wt% is first added in the reaction kettle with stirring, polymer raw is then added simultaneously B and the boron trifluoride ether catalyst for accounting for total material 1.2wt%, react 1.5h at 0 DEG C, after be warming up to 50 DEG C of insulation reactions 2h obtains polymer fluid.Polymer fluid, in 70 DEG C of at a temperature of alkali cleaning, is then washed with clear water to neutrality with 5wt%NaOH aqueous solution, Light yellow resin liquid is obtained, then passes through resin liquid -- under 0.090MPa pressure, temperature is that 290 DEG C of rectifications under vacuum are soft to get arriving Change 91.4 DEG C, Gardner color 5# of point, hydroxyl equivalent (ME) it is 1450.26g/eq, volatile matter≤1.0wt% phenol is modified altogether Poly- Petropols.
Embodiment 8
C10 fraction A, benzenetriol and limonene 1:0.3:0.4 in mass ratio are mixed to get polymer raw B, stirred in band Reaction kettle in the mixed xylenes solvent of total quality of material 40wt% is first added, polymer raw B is then added simultaneously and accounts for total The gas boron trifluoride catalyst of material 0.5wt%, reacts 1.5h at 10 DEG C, after be warming up to 55 DEG C of insulation reaction 2h, obtain Polymer fluid.Then at a temperature of alkali cleaning of the polymer fluid with 5wt%NaOH aqueous solution at 90 DEG C is washed with clear water to neutrality, obtained shallow Yellow coloured resin liquid, then passes through resin liquid -- and under 0.090MPa pressure, temperature is 280 DEG C of rectifications under vacuum to get softening point is arrived 88.8 DEG C, Gardner color 6#, hydroxyl equivalent (ME) it is 475.40g/eq, volatile matter≤1.5wt% phenol modified copolymer petroleum Resin.
Embodiment 9~12
Using C10 fraction A, p-tert-butylphenol PTBP, australene as raw material, hexahydro indane is solvent, gas BF3For catalysis Agent prepares phenol modified petroleum resin, and wherein solvent accounts for the 50wt% of total quality of material, and catalyst amount is total quality of material 0.3wt%.
Embodiment 9 Embodiment 10 Embodiment 11 Embodiment 12
C10 fraction A ratio 1 1 1 1
PTBP ratio 0.1 0.1 0.2 0.2
Australene ratio 0.25 0.5 0.25 0.5
Yield, wt% 36.0 34.7 30.8 28.8
Softening point, DEG C 107.4 93.6 97.5 82.0
Color number, # 4 4 5 5
ME, g/eq 2015.41 1948.66 878.95 789.10
* -10 DEG C of reaction temperature, reaction time 2h, 45 DEG C of holding temperature, soaking time 2h;Resin liquid is pressed in -0.085MPa Under power, temperature is 280 DEG C of rectifications under vacuum.
As seen from the above table, when firpene is as monoene hydrocarbon raw material, resin softening point and color number effect and C5 monoolefine are adjusted It is similar, but the polar intensity of the modified copolymer Petropols obtained obviously increases, hydroxyl equivalent MEIt is opposite to reduce.
Embodiment 13
Resin liquid after alkali cleaning-washing Removal of catalyst can control petroleum tree by different rectifying reduced pressures The volatile matter content of rouge.
As seen from the above table, rectification under vacuum pressure is reduced, raising temperature can reduce the volatile matter of Petropols;For control Resin smell, volatile matter≤2.0, rectifying decompression operation parameter is preferably: pressure -0.085~-0.095MPa, temperature 240~300 ℃。

Claims (9)

1. a kind of preparation method of phenol modified copolymer Petropols, comprising:
(1) by C10 fraction A of the Crude products.deep process C10 raw material rectification under vacuum interception boiling point at 160~210 DEG C, with phenolic monomers with And C5~C10 monoolefine 1:(0.01~0.3 in mass ratio): (0~0.5) is mixed to get polymer raw B;
(2) solvent of total 30~60wt% of material is first added in the reaction kettle with stirring, be then added simultaneously polymer raw B and Friedel-Crafts catalyst is warming up to 30~55 DEG C of 1~3h of insulation reaction after reacting 1.5~3h at -20~30 DEG C, Obtain polymer fluid;
(3) it by polymer fluid alkali cleaning, is washed out to neutrality, obtains resin liquid;Then resin liquid rectification under vacuum is modified to get phenol Copolymerized petroleum resin.
2. a kind of preparation method of phenol modified copolymer Petropols according to claim 1, it is characterised in that: the step (1) component of the C10 fraction A in includes: 5~25wt% of methyl styrene, 5~50wt% of indenes, methyl indenes 5~50wt%, double 0~2wt% of cyclopentadiene, remaining is the saturation aromatic component of C8~C10.
3. a kind of preparation method of phenol modified copolymer Petropols according to claim 1, it is characterised in that: the step (1) phenolic monomers in are phenol, in cresols, hydroquinone, p-tert-butylphenol PTBP, 2- tert-butyl cresols, benzenetriol It is one or more of.
4. a kind of preparation method of phenol modified copolymer Petropols according to claim 1, it is characterised in that: the step (1) C5~C10 monoolefine in is iso-amylene, cyclopentene, 1- amylene, vinylcyclohexene VCH, australene, nopinene, lemon One of alkene.
5. a kind of preparation method of phenol modified copolymer Petropols according to claim 1, it is characterised in that: the step (2) solvent in is one of tetrahydroindene, indane, hexahydro indane, naphthane, or the saturation for boiling point at 80~200 DEG C Aromatic hydrocarbons mixture.
6. a kind of preparation method of phenol modified copolymer Petropols according to claim 1, it is characterised in that: the step (2) the Friedel-Crafts catalyst in is one of gas boron trifluoride, boron trifluoride complex;Catalyst charge For 0.1~3wt% of total material.
7. a kind of preparation method of phenol modified copolymer Petropols according to claim 6, it is characterised in that: the trifluoro Changing boron complex is boron trifluoride ether or boron trifluoride butyl oxide.
8. a kind of preparation method of phenol modified copolymer Petropols according to claim 1, it is characterised in that: the step (3) alkali cleaning in is specially to use the alkali cleaning at 30~90 DEG C of 5wt%NaOH aqueous solution.
9. a kind of preparation method of phenol modified copolymer Petropols according to claim 1, it is characterised in that: the step (3) technological parameter of the rectification under vacuum in are as follows: pressure -0.085~-0.095MPa, 240~300 DEG C of temperature.
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CN109912744A (en) * 2019-03-26 2019-06-21 恒河材料科技股份有限公司 A kind of preparation method of monomer modified C5 Petropols
CN110003388A (en) * 2019-03-26 2019-07-12 恒河材料科技股份有限公司 A kind of preparation method of hydrogenation modification C5 Petropols
CN110563875A (en) * 2019-09-20 2019-12-13 宁波甬华树脂有限公司 Preparation method of modified aromatic hydrocarbon petroleum resin
CN111072854A (en) * 2019-12-26 2020-04-28 广东新华粤石化集团股份公司 Phenol modified C9 petroleum resin and preparation method thereof
CN112063100A (en) * 2020-09-14 2020-12-11 江苏麒祥高新材料有限公司 Modified resin liquid and preparation method thereof
CN114702611A (en) * 2022-05-18 2022-07-05 江苏麒祥高新材料有限公司 Anti-slippery resin and preparation method and application thereof
CN116574216A (en) * 2023-06-08 2023-08-11 青岛伊森新材料股份有限公司 Nine-carbon petroleum resin and preparation method thereof

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Publication number Priority date Publication date Assignee Title
CN109912744A (en) * 2019-03-26 2019-06-21 恒河材料科技股份有限公司 A kind of preparation method of monomer modified C5 Petropols
CN110003388A (en) * 2019-03-26 2019-07-12 恒河材料科技股份有限公司 A kind of preparation method of hydrogenation modification C5 Petropols
CN110003388B (en) * 2019-03-26 2021-09-07 恒河材料科技股份有限公司 Preparation method of hydrogenated modified C5 petroleum resin
CN109912744B (en) * 2019-03-26 2021-10-22 恒河材料科技股份有限公司 Preparation method of monomer modified C5 petroleum resin
CN110563875A (en) * 2019-09-20 2019-12-13 宁波甬华树脂有限公司 Preparation method of modified aromatic hydrocarbon petroleum resin
CN110563875B (en) * 2019-09-20 2021-12-21 宁波甬华树脂有限公司 Preparation method of modified aromatic hydrocarbon petroleum resin
CN111072854A (en) * 2019-12-26 2020-04-28 广东新华粤石化集团股份公司 Phenol modified C9 petroleum resin and preparation method thereof
CN112063100A (en) * 2020-09-14 2020-12-11 江苏麒祥高新材料有限公司 Modified resin liquid and preparation method thereof
CN114702611A (en) * 2022-05-18 2022-07-05 江苏麒祥高新材料有限公司 Anti-slippery resin and preparation method and application thereof
CN114702611B (en) * 2022-05-18 2024-01-02 江苏麒祥高新材料有限公司 Anti-wet-skid resin and preparation method and application thereof
CN116574216A (en) * 2023-06-08 2023-08-11 青岛伊森新材料股份有限公司 Nine-carbon petroleum resin and preparation method thereof

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