CN105482039B - A kind of method that Petropols are prepared by raw material of C9 cuts - Google Patents
A kind of method that Petropols are prepared by raw material of C9 cuts Download PDFInfo
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- CN105482039B CN105482039B CN201511023523.9A CN201511023523A CN105482039B CN 105482039 B CN105482039 B CN 105482039B CN 201511023523 A CN201511023523 A CN 201511023523A CN 105482039 B CN105482039 B CN 105482039B
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- 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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- 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
- C08F4/00—Polymerisation catalysts
- C08F4/06—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen
- C08F4/22—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen of chromium, molybdenum or tungsten
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Abstract
A kind of raising Petropols yield is aimed to provide, shorten the reaction time and improves product quality the invention discloses a kind of method that Petropols are prepared by raw material of C9 cuts, aftertreatment technology is improved, the preparation method of the Petropols of post processing generation environment pollution is reduced；Technical points：This method：1) using the normal heptane of raw material volume 15 25% as solvent, raw material and solvent are added in the reactor with agitating device, the molecular sieve carried phosphotungstic acids of Al MCM 41 are added for catalyst, catalyst amount is 1% the 3% of material quality；2) add nitrogen and enter line replacement, start pressure in stirring, kettle and be set as 0.4 0.9MPa, be heated to 60 100 DEG C, and 5 10h are persistently stirred at this temperature, reaction is finished, and base oil resin is extruded with nitrogen, normal temperature vacuum distillation, recycling design, just C9 Petropols.
Description
Technical field
The present invention provides a kind of preparation method of Petropols, specifically, is that one kind prepares stone using C9 cuts as raw material
The method of oleoresin.
Background technology
C9 Petropols be the accessory substance C9 cuts using cracking ethylene preparation device as primary raw material, gather in the presence of a catalyst
Prepared by closing, or it is subjected to combined polymerization with aldehydes, aromatic hydrocarbons, terpene compound thermoplastic resin.Its molecular mass one
As be less than 2000, softening point be less than 150 DEG C, in thermoplasticity thick liquid or solid.Because its softening point is low, molecular weight compares
It is small, typically it is used alone not as material.Due to not polar functionalities in the structure of C9 Petropols, with good water-fast
Property, resistance to acids and bases, weatherability and light fastness aging, dissolubility in organic solvent is good, and the compatibility with other resins is good, also
Enbrittle, tackifying, caking property and plasticity, be mainly used in coating, rubber chemicals, paper additive, ink and adhesive
Deng field, the huge market demand.
The catalytic polymerization of Petropols is cationic sudden reaction, mainly monomer in the presence of catalyst,
Carbonium ion activated centre is formed, triggers chain polymerization, so that synthesizing petroleum resin：Extent of dissociation of the activated centre by ion pair
Influence is very big, and reaction medium, solvent are different, and activated centre is also different.Most of Petropols synthesis technique uses catalytic polymerization
Method.The reaction temperature of catalytic polymerization is less than 100 DEG C, generally comprises chain initiation, chain growth, chain tra nsfer and chain termination reaction.Catalysis
Agent BF3Or AlCl3It is complexed to form HX types complex ion initiation chain polymerization with ether.Catalyst polymerization advantage is that polymerization temperature is low, gathers
The conjunction time is short, has the disadvantage that catalyst cost is higher, and has to equipment and have waste water generation in corrosion, technical process, product oil tree
Fat color is deeper etc..
The acidic catalyst of polymerisation has sulfuric acid, phosphoric acid and metal halide etc., and it is at most BF to use at present3With
AlCl3.Such catalyst activity is higher, and synthetic resin form and aspect are good, thus are widely adopted.Wherein BF3It is easy to storage, user
Just, melting point resin being improved at a lower temperature, it is easy to removed from polymer, and easily realizing continuous production, activity is moderate,
Color of resin is shallower, but expensive；AlCl3Polymerization activity be higher than BF3, the softening point and yield of resin be higher, and into
This cheap, wide material sources, sewage disposal is easy in production, but catalyst removal is difficult, the easy and alkali formation gel when neutralizing
And be difficult to remove from reaction solution, color of resin is deeper, larger to equipment corrosion.In process of production, denitrating catalyst is a pass
Key link, if catalyst removal is not clean, Petropols hydraulic performance decline is not only resulted in, and influence whole aftertreatment technology
Carry out.The removing of catalyst can also use ammoniacal liquor or anhydrous alkali chemical combination using being washed again after first polymer fluid is decomposed with alkali
The method of thing formation complex compound removes non-aqueous series catalysts.
Catalyst type has a significant effect to the yield and quality of resin, therefore the selection of new catalyst is to improve oil
Resin yield, shortening reaction time and raising product quality, improve aftertreatment technology, reduce the weight that post processing generation environment pollutes
Want means.
The content of the invention
In view of the above-mentioned problems, improving Petropols yield it is an object of the invention to provide one kind, shortening the reaction time and carry
High yield quality, improves aftertreatment technology, reduces the preparation method of the Petropols of post processing generation environment pollution.
In order to solve the above technical problems, the technical scheme that the present invention is provided is such：
A kind of method that Petropols are prepared by raw material of C9 cuts, comprises the steps successively：
1) using raw material volume 15-25% normal heptane as solvent, raw material and solvent are added to agitating device
In reactor, the molecular sieve carried phosphotungstic acids of Al-MCM-41 are added for catalyst, and catalyst amount is the 1%- of material quality
3%
2) add nitrogen and enter line replacement, start pressure in stirring, kettle and be set as 0.4-0.9MPa, be heated to 60-100 DEG C,
And 5-10h is persistently stirred at this temperature, reaction is finished, and base oil resin is extruded with nitrogen, and normal temperature vacuum distillation is reclaimed molten
Agent, just C9 Petropols.
Further, the above-mentioned method that Petropols are prepared by raw material of C9 cuts, described catalyst is used successively
Following methods are made：
1) template cetyl trimethylammonium bromide is taken to be dissolved in deionized water, 35-45 DEG C of stirred in water bath, Ran Houjia
Enter ammoniacal liquor, tetraethyl orthosilicate is added dropwise, while adding aluminium isopropoxide, then in 35-45 DEG C of stirred in water bath 3-5h, liquid is transferred to
In the stainless steel cauldron of polytetrafluoroethyllining lining, in 75-85 DEG C of crystallization 65-80h, filtering is washed with distilled water to neutrality, just
Drying is walked, 450~550 DEG C of roasting 6h in Muffle furnace are put into, removed template method obtains Al-MCM-41；
Wherein：The mass ratio of described template cetyl trimethylammonium bromide, tetraethyl orthosilicate and aluminium isopropoxide is：
1：40：0.4-4；
2) by step 1) obtained Al-MCM-41 carriers, by every gram of Al-MCM-41 carrier, the ratio of 5-7ml Salkowski's solutions
Example mixing, is stirred at room temperature after 12-24 hour, is separated by filtration, and 80~110 DEG C of dryings 8~12 hours are roasted in 450~550 DEG C
Burn the catalyst for the molecular sieve carried phosphotungstic acids of Al-MCM-41 that can obtain Al modifications for 3 hours.
Further, the above-mentioned method that Petropols are prepared by raw material of C9 cuts, described Salkowski's solution is matter
Measure fraction 20-50% phosphotungstic acid ethanol solutions.
Further, the above-mentioned method that Petropols are prepared by raw material of C9 cuts, described C9 cuts boiling range is 70
~190 DEG C.
Compared with prior art, the technical scheme that the present invention is provided has following technological merit：
Course of reaction of the present invention is gentle, and reaction is easily controlled, and overcomes and uses solid AlCl in the prior art3For catalyst
Easily cause the phenomenon of sudden and violent poly- and excessive kettle, prepared C9 petroleum resin products performance is stable, the of a relatively high C9 stones of resin softening point
Oleoresin softening point is 100~120, and colourity is shallower, and softening point is 7~10, and Petropols bromine number is small, acid number ＜ 1, and outward appearance is pale yellow
Color is transparent glossy.Denitrating catalyst is not required to, is not washed with water, the effective emulsion for solving to produce during Removal of catalyst, significantly
Simplify production technology, and do not produce a large amount of waste water, catalyst can Reusability, obtained Petropols indices meet
National standard, can be widely applied to the fields such as paint, traffic paint and printing-ink.
Embodiment
With reference to specific implementation, the claim to the present invention is described in further detail, and anyone is in the present invention
The modification of the limited number of time made in right, still within the claims of the present invention.
Embodiment 1
1g templates cetyl trimethylammonium bromide (CTAB) is taken to be dissolved in 200ml deionized water, in 40 DEG C of water-baths
Stirring.Then 5ml ammoniacal liquor is added, 40g tetraethyl orthosilicates are added dropwise, while adding 4g aluminium isopropoxides, is then stirred in 40 DEG C of water-baths
Mix 4h.Liquid is transferred in the stainless steel cauldron of polytetrafluoroethyllining lining afterwards, in 80 DEG C of crystallization 72h, rear filtering, with steaming
Distilled water is washed to neutrality, is dried.Finally put it into Muffle furnace, 450 DEG C of roasting 6h, removed template method obtains Al-MCM-
41。
The MCM-41 carriers that 5g Al obtained above are modified, add 30ml mass fractions molten for 20% phosphotungstic acid ethanol
In liquid, after stirring 12 hours at room temperature, it is separated by filtration.80 DEG C of dryings 8 hours, are calcined 3 hours in 450 DEG C.Obtaining silica alumina ratio is
10, phosphotungstic acid load capacity is the 20% molecular sieve carried phosphotungstic acid catalysts of Al-MCM-41.
Embodiment 2
1g templates cetyl trimethylammonium bromide (CTAB) is taken to be dissolved in 200ml deionized water, in 40 DEG C of water-baths
Stirring.Then 5ml ammoniacal liquor is added, 40g tetraethyl orthosilicates are added dropwise, while 0.8g aluminium isopropoxides are added, then in 40 DEG C of water-baths
Stir 4h.Liquid is transferred in the stainless steel cauldron of polytetrafluoroethyllining lining afterwards, in 80 DEG C of crystallization 72h, rear filtering is used
Water washing is distilled to neutrality, is dried.Finally put it into Muffle furnace, 500 DEG C of roasting 6h, removed template method obtains Al-
MCM-41。
The MCM-41 carriers that 5g Al obtained above are modified, add 30ml mass fractions molten for 35% phosphotungstic acid ethanol
In liquid, after stirring 18 hours at room temperature, it is separated by filtration.100 DEG C of dryings 10 hours, are calcined 3 hours in 500 DEG C.Obtain silica alumina ratio
For 50, phosphotungstic acid load capacity is the 35% molecular sieve carried phosphotungstic acid catalysts of Al-MCM-41.
Embodiment 3
1g templates cetyl trimethylammonium bromide (CTAB) is taken to be dissolved in 200ml deionized water, in 40 DEG C of water-baths
Stirring.Then 5ml ammoniacal liquor is added, 40g tetraethyl orthosilicates are added dropwise, while 0.4g aluminium isopropoxides are added, then in 40 DEG C of water-baths
Stir 4h.Liquid is transferred in the stainless steel cauldron of polytetrafluoroethyllining lining afterwards, in 80 DEG C of crystallization 72h, rear filtering is used
Water washing is distilled to neutrality, is dried.Finally put it into Muffle furnace, 550 DEG C of roasting 6h, removed template method obtains Al-
MCM-41。
The MCM-41 carriers that 5g Al obtained above are modified, add 30ml mass fractions molten for 50% phosphotungstic acid ethanol
In liquid, after stirring 24 hours at room temperature, it is separated by filtration.110 DEG C of dryings 12 hours, are calcined 3 hours in 550 DEG C.Obtain silica alumina ratio
For 100, phosphotungstic acid load capacity is the 50% molecular sieve carried phosphotungstic acid catalysts of Al-MCM-41.
Embodiment 4
Raw material C9 cuts boiling range is 78~173 DEG C；
Using the normal heptane of raw material volume 20% as solvent, raw material and solvent are added to the reactor with agitating device
In, the catalyst of the preparation of embodiment 1 is added, catalyst amount is the 1% of material quality.Reactor nitrogen enters line replacement,
Start pressure in stirring, kettle and be set as 0.4MPa, be heated to 60 DEG C, and persistently stir 5h at this temperature, reaction is finished, and uses nitrogen
Air pressure goes out rubble oleoresin, and normal temperature vacuum distillation steams light component, and recycling design just can obtain satisfactory C9 oil tree
Fat.It the results are shown in Table one.
Embodiment 5
Raw material C9 cuts boiling range is 78~173 DEG C；
Using the normal heptane of raw material volume 20% as solvent, raw material and solvent are added to the reactor with agitating device
In, the catalyst of the preparation of embodiment 2 is added, catalyst amount is the 3% of material quality.Reactor nitrogen enters line replacement,
Start pressure in stirring, kettle and be set as 0.9MPa, be heated to 100 DEG C, and persistently stir 10h at this temperature, reaction is finished, and is used
Nitrogen extrudes base oil resin, and normal temperature vacuum distillation steams light component, and recycling design just can obtain satisfactory C9 oil
Resin.It the results are shown in Table one.
Embodiment 6
Raw material C9 cuts boiling range is 92~185 DEG C；
Using the normal heptane of raw material volume 20% as solvent, raw material and solvent are added to the reactor with agitating device
In, the catalyst of the preparation of embodiment 3 is added, catalyst amount is the 2% of material quality.Reactor nitrogen enters line replacement,
Start pressure in stirring, kettle and be set as 0.6MPa, be heated to 80 DEG C, and persistently stir 7h at this temperature, reaction is finished, and uses nitrogen
Air pressure goes out rubble oleoresin, and normal temperature vacuum distillation steams light component, and recycling design just can obtain satisfactory C9 oil tree
Fat.It the results are shown in Table one.
Embodiment 7
Raw material C9 cuts boiling range is 92~185 DEG C；
Using the normal heptane of raw material volume 20% as solvent, raw material and solvent are added to the reactor with agitating device
In, add the preparation of embodiment 3 for catalyst, catalyst amount is the 3% of material quality.Reactor is put with nitrogen
Change, start pressure in stirring, kettle and be set as 0.9MPa, be heated to 100 DEG C, and persistently stir 9h at this temperature, reaction is finished,
Base oil resin is extruded with nitrogen, normal temperature vacuum distillation steams light component, and recycling design just can obtain satisfactory C9 stones
Oleoresin.It the results are shown in Table one.
Table one
Claims (4)
1. a kind of method that Petropols are prepared by raw material of C9 cuts, it is characterised in that comprise the steps successively：
1) using raw material volume 15-25% normal heptane as solvent, raw material and solvent are added to the reaction with agitating device
In device, the molecular sieve carried phosphotungstic acids of Al-MCM-41 are added for catalyst, and catalyst amount is the 1%-3% of material quality；
2) add nitrogen and enter line replacement, start pressure in stirring, kettle and be set as 0.4-0.9MPa, be heated to 60-100 DEG C, and
5-10h is persistently stirred at a temperature of this, reaction is finished, with nitrogen extrude base oil resin, normal temperature vacuum distillation, recycling design, i.e.,
Obtain C9 Petropols.
2. the method according to claim 1 that Petropols are prepared by raw material of C9 cuts, it is characterised in that described urges
Agent is made using following methods successively：
1) template cetyl trimethylammonium bromide is taken to be dissolved in deionized water, then 35-45 DEG C of stirred in water bath add ammonia
Water, is added dropwise tetraethyl orthosilicate, while adding aluminium isopropoxide, then in 35-45 DEG C of stirred in water bath 3-5h, liquid is transferred into poly- four
In the stainless steel cauldron of PVF liner, in 75-85 DEG C of crystallization 65-80h, filtering is washed with distilled water to neutrality, preliminary dry
It is dry, 450~550 DEG C of roasting 6h in Muffle furnace are put into, removed template method obtains Al-MCM-41；
Wherein：The mass ratio of described template cetyl trimethylammonium bromide, tetraethyl orthosilicate and aluminium isopropoxide is：1 ﹕
40 ﹕ 0.4-4；
2) by step 1) obtained Al-MCM-41 carriers, are mixed in the ratio of every gram of Al-MCM-41 carrier, 5-7ml Salkowski's solutions
Close, be stirred at room temperature after 12-24 hour, be separated by filtration, 80~110 DEG C of dryings 8~12 hours, in 450~550 DEG C of roastings 3
Hour can obtain the catalyst of the molecular sieve carried phosphotungstic acids of Al-MCM-41 of Al modifications.
3. the method according to claim 2 that Petropols are prepared by raw material of C9 cuts, it is characterised in that described phosphorus
Tungstic acid is mass fraction 20-50% phosphotungstic acid ethanol solutions.
4. the method according to claim 1 that Petropols are prepared by raw material of C9 cuts, it is characterised in that described C9
Cut boiling range is 70~190 DEG C.
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| CN101659733A (en) * | 2009-09-04 | 2010-03-03 | 广东新华粤石化股份有限公司 | Synthesis method of light chroma C9 petroleum resin |
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Effective date of registration: 20220124 Address after: 113000 Heping Village, Tayu Town, Wanghua District, Fushun City, Liaoning Province Patentee after: Fushun Kelong Chemical Industry Co.,Ltd. Address before: 510006 room 515, Hall 4, Guangdong University of technology, No. 100, Waihuan West Road, Guangzhou University, Panyu District, Guangzhou, Guangdong Province Patentee before: GUANGDONG University OF TECHNOLOGY |