CN1269370A - Petroleum resin modified with the by product of styrene and its paint material and production process - Google Patents
Petroleum resin modified with the by product of styrene and its paint material and production process Download PDFInfo
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- CN1269370A CN1269370A CN 00106017 CN00106017A CN1269370A CN 1269370 A CN1269370 A CN 1269370A CN 00106017 CN00106017 CN 00106017 CN 00106017 A CN00106017 A CN 00106017A CN 1269370 A CN1269370 A CN 1269370A
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- resin
- petroleum resin
- vinylbenzene
- styrene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F240/00—Copolymers of hydrocarbons and mineral oils, e.g. petroleum resins
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- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The present invention discloses a method for polymerizing and preparing polystyrene by-product resin and styrene by-product-petroleum resin copolymer resin by using polystyrene by-product, styrene by-product and ethylene cracking by-product as raw material under the action of Friedel-Crafts catalyst. The obtained polystyrene by-product resin is mixed with liquid or solid petroleum resin, and a proper quantity of solvent can be added to the mixture so as to prepare reinforced petroleum resin paint, also a proper quantity of solvent may be added to the styrene by-product-petroleum resin copolymer resin to prepare paint. Said invention overcomes the defects of petroleum resin with poor hue and low strength, and can greatly raise impact-resisting strength of paint film.
Description
The present invention relates to catalyst, prepare polystyrene by product resin by the polymerization of vinylbenzene by product with Friedel-Craft, by the vinylbenzene by product with cracking of ethylene by product C
5And/or C
9Cut copolymerization polystyrene by product modified petroleum resin multipolymer and manufacturing process thereof, and add solvent after with liquid state or solid petroleum mixed with resin by polystyrene by product resin; Or the enhancement type petroleum resin paint vehicle and the technology thereof of adding solvent preparation in the polystyrene by product modified petroleum resin multipolymer.The manufacturing process that belongs to modified petroleum resin and corresponding paint vehicle.
Mainly contain alkene and diolefine and aromatic hydroxy compound in the cracking of ethylene by-product tar, be commonly referred to C
5And C
9Cut, with it is raw material, preparation aliphatics and aromatic hydrocarbons petroleum resin, copolymerized petroleum resin, vinylbenzene-indene resin under Friedel-Crafts catalysts such as Lewis acid, organometallic compound or bimetal initiator, and the further modification of petroleum resin that polymerization is obtained is to enlarge its application, detailed description has been arranged, as contriver's patent ZL96119529.0 here in a large amount of publications and patent.
Usually the petroleum resin that prepare various performances according to the requirement of using.The performance of petroleum resin products is decided by the character and the polymerizing condition of raw mix.A lot of patents relate to improvements over the prior art to improve its performance to be fit to different purposes, mainly are to improve color, softening temperature and with the consistency of rubber and resin etc.Disclose to adopt as US4118555 and italian patent 975795 and will cause darker alkene of color and diolefine prepolymerization earlier, after isolating polymkeric substance, again with raw material polymerization under the Friedel-Crafts catalyst, or with the method for the unsaturated hydrocarbons copolymerization that on average contains 5 carbon atoms, obtain light color and the petroleum resin good with rubber compatibility; US4391961 and US4562233 disclose the distillation of the cracking of ethylene cut of thermal absorption, intercept suitable cut polymeric method, can prepare the Jia Shi color and be 4 light tree oil; US4540480 and US4952635 disclose and have adopted the hydrogenant method to prepare the method for light colour petroleum resin.
US4283581 discloses elder generation with cracking of ethylene by product C
9Cut thermopolymerization, same C under the Friedel-Crafts catalyst again
9The cut copolymerization has the method for petroleum resin to be fit for various uses of various softening temperatures.
US4245075 discloses the technology of turps and the improved turps of petroleum resin copolymerization binding property-petroleum resin multipolymer.
Petroleum resin are that by product with petrochemical iy produced is a feedstock production, the based thermoplastic resin, with rubber and other resins good consistency is arranged, water tolerance, resistance to acids and bases, electrical insulating property and good thermal stability, and low price, thereby be widely used in coating, tamanori, rubber, every field such as glue used in paper-making.The main drawback of the petroleum resin that the employing usual method obtains is that the relatively poor intensity of form and aspect is lower, though by adopting to methods such as further distillation of raw material, solvent extraction and hydrogenations, can improve its form and aspect, but the complex process of these methods, cost an arm and a leg and can not get satisfied result sometimes; The another one shortcoming of petroleum resin is that intensity is lower, generally can not use separately, thereby petroleum resin usually need be with other resin, and rubber or plastics mix and use, as in coating with Synolac, acrylic resin; In tamanori, use jointly with elastomericss such as EVA, SIS.
The objective of the invention is to remedy the deficiencies in the prior art, with the by product tar that production vinylbenzene obtains, the liquid or solid-state vinylbenzene by product homopolymer resin of preparation is turned waste into wealth the vinylbenzene by product under the Friedel-Crafts catalyst.
Another object of the present invention be to provide a kind of by vinylbenzene by product tar with cracking of ethylene by product C
5And/or C
9The copolymer resin of petroleum resin obtains light modified petroleum resin, and can improve the performance of petroleum resin.
A further object of the present invention is by vinylbenzene by product and C
5And/or C
9The solvent that adds suitable kind and quantity in the copolymer resin of petroleum resin, or vinylbenzene by product homopolymer resin and C
5Or/and C
9The homopolymer of petroleum resin or multipolymer mix and are equipped with appropriate solvent, prepare high-performance enhancement type petroleum resin paint vehicle.
Vinylbenzene is basic Organic Chemicals, during industrial production vinylbenzene, often produces by product---vinylbenzene by product tar; During styrene polymerization, also can produce similar by product, below be referred to as the vinylbenzene by product.At present the vinylbenzene by product is not also utilized method preferably, be used as water-proof material as waste, low-grade fuel or replacement pitch substantially.Among the present invention, select the Friedel-Crafts catalyzer for use, will distill or distillatory vinylbenzene or polystyrene by product can not obtain solid or heavy-gravity liquid styrene by product resin 20--200 ℃ of following polymerase 10 .5 to 10 hour.
The vinylbenzene by product can also be with cracking of ethylene by product C
5And/or C
9The cut copolymerization is with to C
5And C
9Petroleum resin carry out modification, specifically, and with the C of 0--70%
5And/or C
9Vinylbenzene by product polymerization under the Friedel-Crafts catalyst of cut and 30--100%, poly-and reaction terminating is put into the still kettle distillation to remove unreacted monomer and solvent after also removing catalyzer, obtains vinylbenzene by product modified petroleum resin multipolymer.
The invention still further relates to a kind of enhancement type petroleum resin paint vehicle of modulating paint, be with the liquid or solid petroleum resin products, the polystyrene by product resin that obtains with the by product vinylbenzene by product polymerization of styrene Production mixes mutually, or selects vinylbenzene by product modification C for use
5And/or C
9The petroleum resin multipolymer, the solvent of adding different fractions, different quantities obtains little Huang to isabelline transparent liquid enhancement type petroleum resin paint vehicle.
Enhancement type petroleum resin paint vehicle of the present invention can also be selected waster terylene silk, the first-class waster terylene of waster terylene cloth for use.After terylene waste material added dissolution with solvents, join again in liquid or the dissolved petroleum coal resin and be modulated into required paint vehicle.
Vinylbenzene by product of the present invention can be that dehydriding is made the by product tar that vinylbenzene obtains behind the benzene-alkylation, also can be the cinnamic by-product tar of additive method or prepared, claims high towards circulation fluid, vinylbenzene waste liquid etc. again.Polystyrene by product resin that polymerization obtains or the form and aspect of copolymer resins (Jia Shi method) are 5-15#; Denseness (cup type viscosity juice) 60～160 seconds; Density: 1-1.5; Acid number≤0.1; Bromine number 16-18.
The raw material of homopolymerization of the present invention or copolymerized petroleum resin is the by product of cracking of ethylene, and boiling point 20-300 ℃ cut during use, requires to distill to intercept corresponding cut or coarse raw materials not distill and direct polymerization according to product performance.
Catalyzer of the present invention can be Lewis acid, organometallics or bimetal organic compound, as the vitriol oil (SA), aluminum chloride (TCA), boron trifluoride (TFB), boron trifluoride ethyl ether complex (TFBEE) aluminum chloride Composite Double cationic catalyst etc., preferred aluminum chloride, boron trifluoride and boron trifluoride ethyl ether complex, catalyst consumption is 0.01-5 ‰ of a monomer weight.
Chain terminator of the present invention can be the aqueous solution, Fatty Alcohol(C12-C14 and C12-C18) or the phosphite etc. of solid alkali, alkali, preferred solid hydrogen calcium oxide or ethanol, and the consumption of chain terminator is 0.5-3%.
Polyreaction of the present invention can be carried out under normal pressure, and temperature of reaction is 20-200 ℃, 0.5 to 12 hour reaction times, the reaction times really normal root decide according to the performance of temperature of reaction, product; Reaction can be carried out under nitrogen protection, also can carry out under air ambient; Can under normal pressure, distill after the reaction, also can underpressure distillation to remove unreacted monomer and solvent; Adopt method of the present invention, can obtain solid, also can obtain liquid resin.
The preparation of paint vehicle of the present invention can select for use the polystyrene by product with solid or liquid C
5And/or C
9Petroleum resin mix, and add an amount of solvent as required again and make, and also can select the same C of vinylbenzene by product for use
5And/or C
9It is formulated that the enhancing petroleum resin that copolymerization obtains add an amount of solvent, when the viscosity of product requires to hang down, can add solvent; When the needs rate of drying is fast, add low boiling point solvent, otherwise add the boiling range high solvent, general solid content is 40-80%.
Prepare paint vehicle solvent for use of the present invention and can be gasoline, benzene class, alkanes, naphthenic hydrocarbon, ether, ketone, alcohol or two or more mixture wherein.
Adopt the enhancing petroleum resin of prepared of the present invention, the product form and aspect are good, and intensity and snappiness height can be used for painting, the production of coating, rubber, tackiness agent and paper, especially can be directly used in and produce paint, and having solved effectively can not be merely with C
5～C
9Petroleum resin are the problem that base-material is produced paint vehicle, the shortcoming that the paint film that has remedied existing petroleum resin paint vehicle is crisp, intensity is low and toughness is low.Directly can meet or exceed the quality standard of similar painting with the paint of this kind enhancement type petroleum resin production.Simultaneously can prepare different denseness according to different needs, the paint vehicle of different rate of dryings has been simplified the production technique of painting.This product can with various organic solvents, acrylic resin, Synolac, resol, rosin and derivative thereof; styrene-butadiene rubber(SBR) etc. mix; and very strong electrical insulating property, acid-alkali-corrosive-resisting, water-fast, photostabilization, the regeneration that can be used to prepare paint, tamanori and rubber are arranged.
This product adds stretching resistance, the secondary tar polymer resin of vinylbenzene that anti-impact force is very strong on the basis of original petroleum resin, improved the performance of petroleum resin, has improved quality product, and has made full use of refuse.
The following stated embodiment describes the present invention in detail, but the present invention is not limited to following examples.Wherein the raw material ethylene cracking tar is provided by Daqing petrochemical company, and the vinylbenzene by product is provided by Fushun Petrochemical Company, and the content among the embodiment is weight percentage.
Embodiment 1
100 kilograms of vinylbenzene by product tar are put into reactor, add 1 ‰ boron trifluoride ethyl ether complexs, polyreaction 3 hours, with 3% calcium hydroxide termination reaction, filter and remove sediment, distillation desolventizes, and obtains solid polystyrene by product resin, and the form and aspect of this polystyrene by product resin (Jia Shi method) are 7#; Bromine number 16-18.
Embodiment 2
With cracking of ethylene by-product tar C
5-C
9Cut distills through normal pressure, 100 kilograms of cuts before getting 200-250 ℃, add the byproduct that produces in 30 kilograms of polystyrene production technique---vinylbenzene by product tar, put into polymeric kettle, add 0.1 ‰ boron trifluoride ethyl ether complex catalyzer, polymerized at room temperature 0.5 hour, add concentration again and be 3% calcium hydroxide and be stirred to light yellowly, filter and remove sediment, put into still kettle and distill, to viscosity for being coated with-4 viscosmeters 20 seconds, iron cobalt color ratio degree 5#.
Embodiment 3
100 kilograms of vinylbenzene by product tar are put into reactor, add 0.5 ‰ boron trifluoride ethyl ether complexs, polyreaction 8 hours, with 1% calcium hydroxide termination reaction, filter and remove sediment, the distillation desolventize to denseness for being coated with-4 viscosmeters 120 seconds, obtain liquid polystyrene by product resin, the form and aspect of this polystyrene by product resin (Jia Shi method) are 7#; Bromine number 16-18.
Embodiment 4-9
Method preparation according to embodiment 1 or 2 sees the following form:
| Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | Embodiment 9 | Embodiment 10 | |
| Styrene accessory substance tar (KG) C5 (KG) C9 (KG) catalyst amount (KG) polymerization temperature ℃ polymerization time Hr terminator consumption viscosity colour | 100 0 0 TFBE 0.1 30 7 NaOH 0.5 140 5# | 40 60 H2SO4 0.4 120 10 Na2CO3 1 40 15# | ??30 ??70 ??TCA ??0.2 ??150 ??5 ??Ca(OH)2 ??1.5 ??100 ??5# | ??50 ??25 ??25 ??TFB ??0.05 ??80 ??8 ??Ca(OH)2 ??2 ??120 ??8# | ??20 ??10 ??70 ??TFBE ??0.1 ??100 ??3 ??Ca(OH)2 ??3 ??80 ??6# | 60 5 35 TFBE, 0.05 180 1 ethanol, 1 60 10 | ??80 ??20 ??TFBE ??0.15 ??60 ??4 ??Ca(OH)2 ??1 ??90 ??4# |
Embodiment 11
With preparation among the embodiment 2 the vinylbenzene by product--petroleum resin copolymer resin 100KG puts into reactor, add 100KG benzene, stir, obtain the vinylbenzene by product--petroleum resin copolymer resin paint vehicle.
Embodiment 12-16
Method according to embodiment 11 prepares paint vehicle.
| Embodiment 12 KG | Embodiment 13 KG | Embodiment 14 KG | Embodiment 15 KG | Embodiment 16 KG | |
| Vinylbenzene by product tar resin styrene tar-C5 C9 copolymer resins | 40 | ?70 | 10 | 30 |
| Styrene tar-C5 copolymer resins styrene tar-C9 copolymer resins Petropols gasoline toluene acetone butanone | 20 40 | ?30 | ?50 ?20 ?20 | ?5 ?40 ?45 ?10 | ?30 ?40 |
Embodiment 17
Performance according to standard testing embodiment 16 paint vehicles the results are shown in following table:
| Styrene tar modified petroleum resin paint vehicle | The petroleum resin paint vehicle | |
| Time of drying (hr), surface drying time of drying (hr) is done solid work shock strength (J) snappiness (mm) hardness water tolerance | ≤ 4≤20 〉=51 〉=0.5 soak the 5hr no change | ≤ 8≤50 〉=2 0.7 〉=0.2 soak the 48hr no change |
Claims (6)
1. vinylbenzene by product modified petroleum resin is characterized in that the waste liquid with the 20-100% production of styrene---the vinylbenzene by product is a raw material, under 0.1-5 ‰ Friedel-Crafts catalysts, with 0-80% ethylene cracking tar C
5And/or C
9Cut, 20-200 ℃ of following polyreaction 0.5 to 10 hour, after polymerization is finished, add 0.5-3% chain terminator stopped reaction, remove behind the sludge normal pressure or underpressure distillation and remove unreacted monomer and solvent, can also add the C of 0-60% in the resin that obtains after the polymerization
5And/or C
9Petroleum resin.
2. catalyzer according to claim 1, can be Lewis acid, organometallics or bimetal organic compound, as the vitriol oil, aluminum chloride, boron trifluoride, boron trifluoride ethyl ether complex or aluminum chloride Composite Double cationic catalyst etc., preferred aluminum chloride, boron trifluoride and boron trifluoride ethyl ether complex.
3. chain terminator according to claim 1 can be the aqueous solution, Fatty Alcohol(C12-C14 and C12-C18) or the phosphite etc. of solid alkali, alkali, preferred solid hydrogen calcium oxide or ethanol.
4. resin according to claim 1 can be a liquid, also can be solid.
5. resin according to claim 1 can be used for paint, coating, rubber, tamanori, preferably as the paint vehicle that paints.
6. the preparation technology of a vinylbenzene by product modified petroleum resin is characterized in that the waste liquid with the 20-100% production of styrene---the vinylbenzene by product is a raw material, under 0.1-5 ‰ Friedel-Crafts catalysts, with 0-80% ethylene cracking tar C
5And/or C
9Cut, 20-200 ℃ of following polyreaction 0.5 to 10 hour, after polymerization is finished, add 0.5-3% chain terminator stopped reaction, remove behind the sludge normal pressure or underpressure distillation and remove unreacted monomer and solvent, can also add the C of 0-60% in the resin that obtains after the polymerization
5And/or C
9Petroleum resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001060171A CN1137163C (en) | 1999-04-01 | 2000-04-03 | Petroleum resin modified with the by product of styrene and its paint material and production process |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99103546.1 | 1999-04-01 | ||
| CN99103546 | 1999-04-01 | ||
| CNB001060171A CN1137163C (en) | 1999-04-01 | 2000-04-03 | Petroleum resin modified with the by product of styrene and its paint material and production process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1269370A true CN1269370A (en) | 2000-10-11 |
| CN1137163C CN1137163C (en) | 2004-02-04 |
Family
ID=25739272
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB001060171A Expired - Fee Related CN1137163C (en) | 1999-04-01 | 2000-04-03 | Petroleum resin modified with the by product of styrene and its paint material and production process |
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| Country | Link |
|---|---|
| CN (1) | CN1137163C (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100462382C (en) * | 2006-10-09 | 2009-02-18 | 中国石油兰州石油化工公司 | CS petroleum resin quick-functionizing method |
| CN106008818A (en) * | 2016-06-26 | 2016-10-12 | 广西众昌树脂有限公司 | Preparation method of petroleum resin |
| CN106956314A (en) * | 2017-04-28 | 2017-07-18 | 广州铁路职业技术学院 | A kind of efficient vegetable cutting machine cut into slices and method of cutting the dish |
| CN107759812A (en) * | 2017-10-10 | 2018-03-06 | 深圳大学 | Cross-linked polymer based on waste polystyrene and preparation method and application |
-
2000
- 2000-04-03 CN CNB001060171A patent/CN1137163C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100462382C (en) * | 2006-10-09 | 2009-02-18 | 中国石油兰州石油化工公司 | CS petroleum resin quick-functionizing method |
| CN106008818A (en) * | 2016-06-26 | 2016-10-12 | 广西众昌树脂有限公司 | Preparation method of petroleum resin |
| CN106956314A (en) * | 2017-04-28 | 2017-07-18 | 广州铁路职业技术学院 | A kind of efficient vegetable cutting machine cut into slices and method of cutting the dish |
| CN106956314B (en) * | 2017-04-28 | 2018-10-19 | 广州铁路职业技术学院 | A kind of efficient vegetable cutting machine being sliced and method of cutting the dish |
| CN107759812A (en) * | 2017-10-10 | 2018-03-06 | 深圳大学 | Cross-linked polymer based on waste polystyrene and preparation method and application |
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| Publication number | Publication date |
|---|---|
| CN1137163C (en) | 2004-02-04 |
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