CN1451021A - Petroleum resins and thir production with BF3 catalyst - Google Patents
Petroleum resins and thir production with BF3 catalyst Download PDFInfo
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- CN1451021A CN1451021A CN00810555A CN00810555A CN1451021A CN 1451021 A CN1451021 A CN 1451021A CN 00810555 A CN00810555 A CN 00810555A CN 00810555 A CN00810555 A CN 00810555A CN 1451021 A CN1451021 A CN 1451021A
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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
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
-
- 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
-
- 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
- C08F4/02—Carriers therefor
- C08F4/025—Metal oxides
-
- 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
- C08F4/12—Metallic 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
- C08F4/14—Boron halides or aluminium halides; Complexes thereof with organic compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J107/00—Adhesives based on natural rubber
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
- C08L2666/04—Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
Abstract
Petroleum resins are produced using a supported BF3 cocatalyst complex. Preferably the cocatalyst is organic such as an alcohol or a carboxylic acid. Use of the catalyst in supported form together with the cocatalyst enables control over both Bronsted and Lewis acidity leading to better control of resin properties. Waste disposal and catalyst handling problems are also overcome.
Description
The improved resin that the present invention relates to preparation method of petroleum resin and prepare thus.
Petroleum resin are that Fred-Ke Laifu polymerizations known and by various raw materials prepare, and described raw material can be the raw material of pure monomer or the refinery stock that contains various unsaturated material blends stream.Typical raw material is C
4-C
6Or C
8-C
9Alkene and diolefine raw material and composition thereof and various pure olefinic monomer.
Resulting hydrocarbon resin can change to hard and crisp solid from sticking liquid, and color can change to light yellow, amber or dun from water white transparency, and this depends on employed monomer and concrete reaction conditions.Typically, pure monomer resin tends to water white transparency, C
9Monomer resin tends to brown, C
5Monomer resin tends to yellow.
Hydrocarbon resin is used in tackiness agent, rubber, hot-melt coating, printing-ink, paint, earth material, road sign and polymkeric substance and other application.This resin is generally used for other material of modification.
Can use Fred-Ke Laifu polymerizing catalyst such as non-loading type Lewis acid (as boron trifluoride (BF
3), the complex compound of boron trifluoride, aluminum chloride (AlCl
3), the chlorination aluminum alkyls), the cationoid polymerisation of the styrene-based monomers by vinylbenzene of replacing as vinylbenzene, alpha-methyl styrene, Vinyl toluene and other alkyl and so on is with the hydrocarbon resin of preparation pure monomer.
Similarly, can be by containing C
4, C
5And C
6The cracking petroleum fraction of paraffins, alkene and diolefine (also is known as " C
5Monomer ") cationoid polymerisation prepare aliphatic C
4-C
6Hydrocarbon resin.These raw material monomer streams are as 1 by cationically polymerizable monomers, the 3-pentadiene, and divinyl, cyclopentenes, amylene, 2-methyl-2-butene, 2-methyl-2-amylene, isoprene, cyclopentadiene and dicyclopentadiene composition, wherein 1,3-pentadiene is main active ingredient.Use Fred-Ke Laifu polymerizing catalyst such as carrier free Lewis acid (as boron trifluoride (BF
3), the complex compound of boron trifluoride, aluminum chloride (AlCl
3) or the chlorination aluminum alkyls) catalytic polymerization.Except active ingredient, the not polymerizable components in the raw material comprises saturated hydrocarbons, described saturated hydrocarbons can with unsaturated component such as pentane, pentamethylene or 2-methylpentane condistillation.This raw material monomer can with C
4Or C
5Alkene or dimer copolymerization.
Can pass through aromatics C
8, C
9And/or C
10Unsaturated monomer (also is known as " C
9Monomer ") cationoid polymerisation prepare aromatics C
9Hydrocarbon resin, described unsaturated monomer derive from the resulting petroleum fractions of petroleum naphtha cracking.These raw material monomer streams typically are made of other alkyl-substituted derivatives of described polymerisable monomer such as vinylbenzene, alpha-methyl styrene, Beta-methyl vinylbenzene, Vinyl toluene, indenes, dicyclopentadiene, Vinylstyrene and these components the mixture of cationically polymerizable monomers.Except active ingredient, polymerizable components does not comprise aromatic hydrocarbons such as dimethylbenzene, ethylbenzene, cumene, ethyltoluene, indane, methyl indenes, naphthalene and other similar species.
Although the carrier free Lewis acid is the cationic polymerization catalyzer that effectively prepares hydrocarbon resin, also there are some disadvantages in they.Conventional carrier free Lewis acid is single catalyst for application, and it requires to make reaction quencher and antacid processing step.
And conventional carrier free Lewis acid also requires to remove the residue of catalyzer salt from resulting rosin products.In case remove the salt residue that produces from catalyst neutralisation, the processing of these residues is unfavorable and cost increase to environment.Therefore, reduce catalyst residue quantity, especially the quantity of the halogen-containing materials that is produced in these reactions is especially interesting.
Use conventional carrier free lewis acid catalyst, as AlCl
3And BF
3Another problem that is involved is that they are deleterious materials.In a single day these conventional lewis acid catalysts are exposed to moisture, then produce the sour gas (as HF, HCl) of high corrosion, therefore are necessary strict dry these raw materials before polymerization.
Therefore, the present invention seeks to overcome these problems, and provides a kind of industrial feasible especially from C
5-C
6Or C
8-C
9Refinery stock stream or its mixture technology of preparing petroleum resin, the conventional impurity in the described technology tolerable raw material reduces the catalyst residue in the resin, and does not need to spend huge catalyst treatment.
The Fred of working load of the present invention-Ke Laifu catalyzer.In the open WO95/26818 of PCT, hinted that the lewis acid catalyst of load can be used for hydrocarbon conversion reactions, comprising the polymerization of unsaturated monomer such as 1,3-pentadiene.Recently, the metal halide catalyst that the open WO98/130587 of PCT has been specifically related to load is used for the preparation of hydrocarbon resin, and WO98/130587 relates generally to the halide catalyst that uses zinc, zirconium and aluminium.
Yet we find that the boron trifluoride catalyst of specific load obtains having the new resin of required improvement performance when using with specific raw material.
Usually, when using the boron trifluoride catalyst of complexing or non-form complexed, be necessary strict dry reaction raw material.We find, when using the boron trifluoride catalyst of particular type, can allow to have moisture in the raw material, and in some cases, this still are useful.
Therefore, we find, boron trifluoride catalyst by working load, may command catalyst performance and use catalyzer high productivity prepare petroleum resin, interior, complexing has taken place in described boron trifluoride catalyst and organic or inorganic promotor comprising some the nonpetroleum resin with special perfect performance.The catalyzer that the application of boron trifluoride complex makes the better control of the strength of acid of catalyzer and allows working strength to increase.Especially, we find, when using the petroleum resin that prepare in this mode in the adhesive formula of adhesive matrix and metal, can obtain highly to tolerate the binder composition of shear conditions.We also find, when using with natural rubber, compare with the resin that uses other conventional catalyst system preparation, can obtain to have the tackiness agent of bonds well power with the resin of lower molecular weight.
Therefore, by polymerization C
5-C
6And/or C
8-C
9Unsaturated hydro carbons raw material, the invention provides a kind of method for preparing petroleum resin, wherein said raw material contacts with the boron trifluoride promotor complex compound of load under polymerizing condition.
The boron trifluoride catalyst of preferred load is disclosed in the theme of Chemical Communications 1998,2135 and 2136 pages and PCT patent disclosure WO00/13792.
Preferred catalyzer is a kind of boron trifluoride complex of novel, load, and its shows Bronsted and lewis acidity, by changing the person's character and the above-mentioned two kinds of acidity of maturing temperature tunable of promotor, carrier.In many organic reactions, the catalytic activity of homogeneous phase boron trifluoride complex depends on complex compound [H
+] [X:BF
3 -] ability, wherein X is a complexing agent, it serves as the proton donor of alkene.The activity of observing promotor in the homogeneous system (HX) reduces in the following order:
HF＞H
2SO
4＞H
3PO
4＞C
6H
5OH＞H
2O＞RCOOH＞ROH
Silicon-dioxide is a kind of preferred support of the catalyst.We have now found that, by at SiO
2The polarizable proton boron trifluoride complex of giving that last load is different can be realized the adjusting of catalytic activity, and be easy to realize the catalyst recovery of heterogeneous solid acid.The thermal treatment of catalyzer subsequently also can be adjusted the relative quantity of existing Lewis acid and bronsted acid sites in addition, and is as described below:
Wherein HX is a complexing ligand.Broensted acidity results from polar δ usually in the solid acid catalyst
-O-H δ
+The site.Observe adhering to of Lewis acid centers and carrier caused strong broensted acidity and give the credit to the polarization of the surface hydroxyl that inductive effect produced of lewis acidic electronegativity halogen atom on sour site, wherein said carrier for example is the carrier with free oxide on surface or hydroxyl.In our preferred system, extra broensted acidity is from above-mentioned Bronsted complex compound.
By changing the person's character of complexing ligand HX and carrier, can change the acidity of Bronsted complex compound.The pka of preferred complexing ligand is between 2.0-4.5.Ethanol and acetate are especially favourable complexing agents.If complexing ligand acidity is too strong, system instability then; If alkalescence is too strong, then catalytic activity reduces.The preparation complex compound during employed solvent (described solvent also can with BF
3Complexing) selection can change the acid matter of catalyzer.Compare with aprotic solvent (ether, aromatic hydrocarbons), protonic solvent (alcohol) can cause the broensted acidity that increases.Employed solvent is preferred predrying to avoid BF in the preparation
3The hydrolysis of complex compound.These solid acids are characterized Bronsted or the Lewis acid characteristic that to measure different catalysts by MAS-NMR, DRIFTS and pyridine titration.We expect that also the thermostability of catalyst complex of these loads can change with employed precursor.Therefore, can adjust Bronsted by preroasting carrier under inert atmosphere: the relative quantity in Lewis acid site.
Prove that by following four kinds of different catalyst systems promotors and solvent to the influence of the broensted acidity of resulting solid acid catalyst, have illustrated this point.
A) to dry 24 hours 100ml dehydrated alcohol and 10g K100 SiO under 300 ℃
2Add BF in the formed slurry
3(H
2O)
2(4.1g, 0.04mol).Under the nitrogen gas stream of room temperature, 50ml/min, stirred the mixture 2 hours.Then slurry is transferred in the rotatory evaporator, descended dry 4 hours to remove all ethanol at 50 ℃.
B) to dry 24 hours 100ml dry toluene and 10g K100 SiO under 300 ℃
2Add BF in the formed slurry
3(H
2O)
2(4.1g, 0.04mol).Under 25 ℃, the nitrogen gas stream of 50ml/min, stirred the mixture 2 hours.Then slurry is transferred in the rotatory evaporator, descended dry 4 hours to remove all toluene at 50 ℃.
C) to dry 24 hours 100ml toluene and 10g K100 SiO under 300 ℃
2Add BF in the formed slurry
3(OEt
2) (5.6g, 0.04mol).Under the nitrogen gas stream under refluxing, at 50ml/min, stirred the mixture 2 hours.Then slurry is transferred in the rotatory evaporator, descended dry 4 hours to remove all toluene at 50 ℃.
D) to dry 24 hours 100ml dehydrated alcohol and 10g K100 SiO under 300 ℃
2Add BF in the formed slurry
3(OEt
2) (5.6g, 0.04mol).Under the nitrogen gas stream of room temperature, 50ml/min, stirred the mixture 2 hours.Then slurry is transferred in the rotatory evaporator, descended dry 4 hours to remove all ethanol at 50 ℃.
The sign of catalyzer
A) BF that uses DRIFTS and characterize load in conjunction with the pyridine titration
3/ SiO
2The characteristic of catalyzer shows that all catalyzer show Lewis acid and broensted acidity.This is by in the DRIFTS spectrum, 1445 and 1461cm
-1(Lewis acid site), 1638 and 1539cm
-1(bronsted acid sites), 1611 and 1489cm
-1(blended lewis acid/bronstead acid site) observed absorption spectrum in place is brought definite.According to the Preparation of catalysts process, there is marked difference in the characteristic in sour site, and the catalyzer that wherein prepares in ethanol demonstrates higher bronsted acid sites concentration than the catalyzer for preparing in toluene.
B) origin cause of formation in sour site on the catalyzer of use thermogravimetry and segregation gas FTIR (TGIR) method research ethanol preparation, wherein desorbed molecule can be by its vibrational spectrum affirmation from catalyzer during heat is analyzed.These two kinds of catalyzer are heated to cause significant weightlessness more than 100 ℃, in IR, observe the alcoholic acid desorb.Yet differential weightlessness shows that ethanol is from BF
3(H
2O)
2/ SiO
2The temperature ratio of middle desorb is from BF
3.OEt
2/ SiO
2The temperature of middle desorb is high 10 ℃, emits the ethanol of about 2 times of amounts.The absorption of short chain alcohol can be used as the index of bronsted acid sites intensity and concentration.Therefore, these results show: with BF
3.OEt
2/ SiO
2Compare BF
3(H
2O)
2/ SiO
2Have the higher distribution of stronger bronsted acid sites.Further heating surpasses 400 ℃ and causes other weightlessness, and described weightlessness accompanies with effusion HF from catalyzer.
C) under nitrogen atmosphere, 200-400 ℃ catalyzer is arrived in roasting, and the titration of its corresponding D RIFTS/ pyridine shows: along with the rising of maturing temperature, lose gradually in the Bronsted site.In case alcohol desorption is complete, the most significant reduction can take place in broensted acidity.
Alcoholic acid is overflowed and the forfeiture of the broensted acidity followed shows: BF when being higher than 100 ℃
3(H
2O)
2/ SiO
2Bronsted acid sites may derive from the BF of ethanol and load in the catalyzer
3The bonding at center, described bonding causes having formed [SiOBF
3]
-[EtOH
2]
+Complex compound.Support the further evidence of this model to come from prepared catalyzer
1H MAS NMR spectrum, it 1.34,4.01 and 8.16ppm place show and resonate, this respectively with protonated alcoholic acid CH
3, CH
2And OH
2 +Consistent.BF has been reported in research in the past
3.OEt
2And the ligand exchange between the ethanol causes having formed H
+[BF
3OEt]
-Complex compound.Yet,, require and more protonated BF in order to form the protonated ethanol complex that is proposed in this model
3Complex compound interacts, as BF
3(H
2O)
2, it can be with [H
3O]
+[BF
3OH]
-Exist.Thereby soluble BF
3.OEt
2And BF
3(H
2O)
2Viewed broensted acidity trend between the precursor.After 200 ℃ of following roastings, from BF
3(H
2O)
2/ SiO
2The ethanol of overflowing in the catalyzer has reduced with the titratable Bronsted of pyridine site quantity.We are interpreted as BF in the Bronsted site that those are residual
xThe polarization of the carrier upper surface hydroxyl that the center causes causes.The dehydroxylation of carrier under 400 ℃ further reduced the Bronsted number of sites, stays the characteristic based on Lewis acid, and this gives the credit to residual BF
xThe site.Observe by TGIR that HF overflows when being higher than 400 ℃, this shows these BF
xGroup begins when being higher than this temperature to decompose, and during to 600 ℃, does not have titratable sour site residual, and this shows BF
xDecompose fully at the center.
Therefore, the person's character of balance carrier, BF
3The person's character of source, promotor and the ability of the Preparation of catalysts method person's character and the character rich diversity of giving catalyzer.This can embody from the performance of using the prepared resin of catalyst system of the present invention.
Therefore, on the one hand, the invention provides a kind of improved method and prepare conventional resin; Second aspect the invention provides a kind of new petroleum resin.Especially when using blended aliphatic series/aromatic raw material to finish when of the present invention,, compare, can in prepared product, mix the aromatic materials of higher amount with using other catalyzer for concrete raw material.For example, we can be had the softening temperature that is higher than 80 ℃, be contained the resin greater than 35% aromatic substance (by the NMR test, as cinnamic Equivalent) by the preparation of this raw materials mixed.Use catalyst system of the present invention can prepare the resin that contains aromatic substance of any required aromatic content, wherein aromatic content can be up to 100%.We think that this can be reflected on the improved bond properties that is obtained when using this resin as tackifier.
On the other hand, the prepared petroleum resin of the present invention are at binding system, as being used as tackifier in solvent-based adhesive, hotmelt and the pressure sensitive adhesive.In these binding systems, petroleum resin serve as the tackifier of employed other polymkeric substance and rubber in the binding system.Person's character and its concrete application of tackiness agent depended in the selection of polymkeric substance and/or rubber.For example, hotmelt is normally based on the multipolymer that contains ethene, especially the multipolymer of Ethylene/vinyl acetate.Pressure sensitive adhesive is normally based on natural or synthetic rubber such as styrene-butadiene-copolymer rubber, and solvent-based adhesive can be aqueous emulsion or organic solvent based tackiness agent, although since environment reason, preferred Aquo System.The example of useful polymeric system is polyacrylic ester and polymethacrylate emulsion in these aqueous binder systems.We find that when using, when especially shearing, resin of the present invention has especially good shear stability on metal and cardboard in pressure sensitive adhesive.
Polymerizing condition is the standard conditions of preparation petroleum resin, should select according to the person's character for the treatment of the polymeric raw material and the desired final performance of resin.
The selection of the manufacture method of support of the catalyst, catalyzer and the selection of promotor are also depended on and are treated polymeric raw material and required resin property.Promotor can be that the organic or inorganic compound is as alcohol, carboxylic acid (preferred acetate), phosphoric acid or water.Can select these two kinds of materials of carrier and promotor aspect following, to increase handiness: by changing person's character, preparation method and the promotor of carrier, can change the ratio of lewis acidity and broensted acidity, preparation is fit to the catalyzer that preparation has the resin of specific desired properties.
We find, for the high-quality petroleum resin of preparation, the BF of these loads
3The promotor complex compound is effectively, need not traditional catalyst residue and removes step.On the one hand, at C
4-C
6And/or C
8-C
9Can use this class catalyzer in the polymerization of raw material, but they are particularly useful in containing the polymerizable raw material of unsaturated aromatic monomer.These monomers can be pure monomer such as alpha-methyl styrene and Vinyl toluene or the petroleum that contains the mixture of unsaturated aromatic materials.When described raw material contains mixture with different rates polymeric monomer such as alkene and diolefine, use the BF of load of the present invention
3/ co-catalyst system can produce greater flexibility.We find that the present invention can make blended C
9Raw material 100% changes into aromatic petroleum resin.Unsaturated aromatic monomer can with other unsaturated material copolymerization, especially C
4-C
6Unsaturated material, described material can be formed petroleum of these mixtures of material or pure C
5Monomer.Purposes according to resin is selected feedstock composition.We find that also these catalyzer are effectively, need not strong dried feed, and this are necessary in the past.
Before the use, solid acid catalyst and/or carrier be can handle, the acidity and the active maximization of catalyzer made to remove and the associating water of the associating freedom of solid.For example, before the use, the competent time of baked solid acid catalyst and/or carrier is to remove free associating water and/or catalyzer and/or carrier are exposed to decompression down.For example, roasting can be to reach 700 ℃ temperature, preferred 50-500 ℃ temperature.Roasting under reduced pressure reaches 8 hours, preferred 1-4 hour.
The person's character of carrier also is important.It must energy and BF
3The reaction and can select according to person's character, promotor and the required resin property of raw material.The example of suitable carriers be contain the material of surface hydroxyl such as silicon-dioxide, synthetic silica (MCM), as Nature 1,992 359, disclosed six side's mesoporous silica (HMS) and clay carrier among the 865th page of the 710th page and the Science267 comprise that naturally occurring clay mineral is as being selected from least a component in kaolin, wilkinite, attapulgite, montmorillonite, clarite (clarit), Fuller's earth, hectorite and the beidellite; Synthesis of clay is as being selected from least a component of talcum powder and hydrotalcite; With the montmorillonitic clay that is selected from least a component processing in sulfuric acid and the hydrochloric acid; And modified clay, comprise being selected from aluminum oxide cylindricality clay, cerium modified aluminum oxide cylindricality clay and at least a component of metal oxide cylindricality clay.Preferred carrier have can with the surface hydroxyl of boron trifluoride reaction.Mesoporous silica is especially preferred carrier.
Carrier also can comprise at least a component that is selected from zeolite beta, zeolite Y, X zeolite, MFI, MEL, NaX, NaY, faujusite, mordenite, aluminum oxide, zirconium white, titanium dioxide and the silico-aluminate.
But also roasting carrier.We find that when using silica supports, roasting changes the character of the surface hydroxyl on the silicon-dioxide.Roasting causes being separated from each other of vicinal hydroxyl groups, this cause with boron trifluoride between produce different interactions, this causes different polyreactions again.Find that roasting can improve the productive rate of resin and reduce the formation of known low molecular weight by-products as weighting material.
The aperture of carrier should make that monomer can be near catalytic species.And the aperture should make the polymer resin that it is difficult in a single day being formed fill up.We find that in order to obtain satisfied resin productive rate, the aperture should at least 100 dusts." aperture " is the narrowest cross section of finger-hole.This can be the diameter or the pore-throat of hole, and in some cases, described pore-throat is narrower than hole.
The catalyst consumption of load also has material impact to the resin property that is obtained on carrier.We find that productive rate increases with the increase of the catalyzer of load, and when the catalyzer of load reached certain load capacity, the molecular resin amount all can be controlled well.The content of optimizing depends on the boron trifluoride/person's character of promotor complex compound and the person's character of carrier, yet when being higher than this certain content, the molecular resin amount of uncontrollable molecular weight and preparation is too high.When the boron trifluoride of working load on K100 silicon-dioxide/ethanol complex catalyzer, productive rate is increased to about 4mmole BF with the catalyzer of load among the embodiment
3/ g and increasing, but under higher load capacity situation, preparation be this high molecular weight material.This is considered to be under these higher load capacity situations, has unsupported catalyst and at least to a certain degree down, this system is operated as homogeneous system.
Feedstream can comprise the monomer of 20wt%-80wt% and the solvent of 80wt%-20wt%.Preferably, feedstream comprises 30wt%-70wt% monomer and 70wt%-30wt% solvent.More preferably, feedstream comprises about 50wt%-70wt% monomer and 50wt%-30wt% solvent.Solvent can comprise a kind of aromatic solvent.This aromatic solvent can comprise at least a component that is selected from toluene, dimethylbenzene and the aromatic petroleum solvent.This solvent can comprise a kind of aliphatic solvents.This solvent can be not polymerisable component in the raw material.The present invention can further comprise the recovery solvent.
On the one hand, feedstream comprises C at least
5Monomer.Optionally, can carry out the fractionated mode, from feedstream, remove cyclopentadiene and methyl cyclopentadiene component by heating under 100-160 ℃ temperature with by distillation.C
5Monomer can comprise and is selected from divinyl, iso-butylene, 2-methyl-2-butene, 1-amylene, 2-Methyl-1-pentene, 2-methyl-2-amylene, 2-amylene, cyclopentenes, tetrahydrobenzene, 1,3-pentadiene, 1,4-pentadiene, isoprene, 1,3-hexadiene, 1, at least a component in 4-hexadiene, cyclopentadiene and the dicyclopentadiene.Feedstream can comprise C at least
5Monomer.Preferred feedstream comprises at least the polymerisable monomer of 70wt% and at least about 50wt%1, the 3-pentadiene.Feedstream can contain a small amount of isoprene.It contains part 2-methyl-2-butene usually and can contain one or more cyclodiene.
Feedstream can further comprise and reaches the 40wt% chain-transfer agent, preferably reaches the 20wt% chain-transfer agent.This chain-transfer agent can comprise and is selected from C
4Alkene, C
5Alkene, C
4The dimer of alkene and C
5At least a component in the dimer of alkene.This chain-transfer agent can comprise at least a component that is selected from iso-butylene, 2-methyl-1-butene alkene, 2-methyl-2-butene and dimer and oligopolymer.
On the other hand, feedstream comprises 30wt%-95wt%C
5Monomer and 70wt%-5wt% auxiliary material (co-feed), described copolymerization raw material comprise and are selected from pure monomer, C
9At least a component in monomer and the terpenes.Preferably, feedstream comprises 50wt%-85wt%C
5Monomer and 50wt%-15wt% copolymerization raw material, described copolymerization raw material comprise and are selected from pure monomer, C
9At least a component in monomer and the terpenes.
On the other hand, feedstream comprises C at least
9Monomer.C
9Monomer can comprise at least a component that is selected from vinylbenzene, Vinyl toluene, indenes, dicyclopentadiene and the alkyl derivative thereof.C
9Monomer can comprise the polymerisable unsaturated hydro carbons of 20wt% at least.C
9Monomer can comprise the polymerisable unsaturated hydro carbons of 30wt%-75wt%, typically the polymerisable unsaturated hydro carbons of 35wt%-70wt%.
The pure monomer feedstream can contain pure relatively styrene-based monomers part as vinylbenzene, alpha-methyl styrene, Beta-methyl vinylbenzene, 4-vinyl toluene and Vinyl toluene cut.This monomer can use with pure component or with the form of the mixture of two or more raw material monomers, thereby obtains required resin property.Preferred mixture comprises 20wt%-90wt% alpha-methyl styrene and one or more comonomers of 80wt%-10wt%, the mixture of optimization styrene, Vinyl toluene, 4-vinyl toluene or these components.In addition, other alkylated styrenes such as t-butyl styrene or styryl phenyl can be used as monomer of the present invention and use.
On the one hand, feedstream comprises 30wt%-95wt%C again
9Monomer and 70wt%-5wt% copolymerization raw material, described copolymerization raw material comprise and are selected from pure monomer, C
5At least a component in monomer and the terpenes.Preferably, feedstream comprises 50wt%-85wt%C
9Monomer and 50wt%-15wt% copolymerization raw material, described copolymerization raw material comprise and are selected from pure monomer, C
5At least a component in monomer and the terpenes.
According to another characteristics of the present invention, in feedstream, add catalyzer.
According to characteristics more of the present invention, in the catalyst slurry in solvent, add feedstream.Can the flow through fixed bed of catalyzer of feedstream.
According to characteristics more of the present invention, feedstream is in the slurry supply response device of catalyzer.
Carry out polymerization with successive technology or technology intermittently.Under temperature of reaction, the reaction times in the batch technology is 30 minutes-8 hours, and preferred 1 hour-4 hours, described temperature of reaction was between-50 ℃-150 ℃, between preferred-20 ℃-100 ℃, more preferably between 0 ℃-70 ℃.Can stop polyreaction by the mode of from hydrocarbon resin, removing catalyzer.Can from hydrocarbon resin, remove catalyzer by filtering.Can from fixed-bed reactor, remove comprising the hydrocarbon resin of catalyzer and can remove unreacted monomer, solvent and low-molecular-weight oligomer by stripping.Recyclable unreacted monomer, solvent and low-molecular-weight oligomer.
Can select feedstream according to required hydrocarbon resin performance.For example, feedstream can comprise C at least
5Monomer, wherein the softening temperature of resulting hydrocarbon resin is between 50 ℃-150 ℃.Alternatively, feedstream can comprise C at least
9Monomer, wherein the softening temperature of resulting hydrocarbon resin is between 70 ℃-160 ℃.
The preferred characteristics according to the present invention, feedstream comprises pure at least monomer, wherein the number-average molecular weight of resulting hydrocarbon resin (Mn) scope is 400-2000, weight-average molecular weight (Mw) scope is 500-5000, Z-average molecular weight (Mz) scope is 500-10000, and the polymolecularity measured according to Mw/Mn (PD) be between about 1.5-3.5, and wherein Mn, Mw and Mz measure according to size exclusion chromatography (SEC).
According to another characteristics of the present invention, feedstream comprises C at least
5Monomer, wherein the number-average molecular weight of resulting hydrocarbon resin (Mn) scope is 400-2000, weight-average molecular weight (Mw) scope is 500-3500, Z-average molecular weight (Mz) scope is 700-15000, and the polymolecularity measured according to Mw/Mn (PD) be between about 1.5-4, and wherein Mn, Mw and Mz measure according to size exclusion chromatography (SEC).
According to characteristics more of the present invention, feedstream comprises C at least
9Monomer, wherein the number-average molecular weight of resulting hydrocarbon resin (Mn) scope is 400-1200, weight-average molecular weight (Mw) scope is 500-2000, Z-average molecular weight (Mz) scope is 700-6000, and the polymolecularity measured according to Mw/Mn (PD) is between about 1.5-3.5, preferred 1.5-2.5, wherein Mn, Mw and Mz measure according to size exclusion chromatography (SEC).
The boron trifluoride promotor complex compound of load can be included on the carrier of single type or compound type the BF in conjunction with any single type or compound type
3With can with one or more reagent complexings.Preferred BF
3With water or organic compound, particularly alcohol is as methyl alcohol, ethanol and propyl alcohol or carboxylic acid such as acetate, propionic acid or butyric acid complexing.
Expection can temperature or time when taking place as the control calcination steps, can realize the physicals of resulting resin such as the control of softening temperature or molecular weight by the condition of control catalyst roasting.
Different with the employed Friedel-Crafts catalyst of previously presented preparation hydrocarbon resin, the BF of load used in the present invention
3It is the most effective that promotor exists under the situation of less water in feedstream.Therefore, they can be used under the situation that need not costliness, strict dried feed.
As for C
5Raw material monomer stream, except reactive component, in the raw material not polymerisable component can comprise can with saturated hydrocarbons such as pentane, pentamethylene or the 2-methylpentane of unsaturated component condistillation.This raw material monomer can with the C as chain-transfer agent
4Or C
5Alkene or dimer copolymerization.With independent use C
5The resin of monomer preparation is compared, and adds that chain-transfer agent can obtain lower molecular weight and than the resin of narrow molecular weight distributions.Chain-transfer agent stops the growth of the polymer chain of growth by chain termination, and described growth is to carry out in the mode that produces polymkeric substance initiation position again.The component of serving as chain-transfer agent in these reactions includes but not limited to the dimer or the oligopolymer of iso-butylene, 2-methyl-1-butene alkene, 2-methyl-2-butene or these species.Chain-transfer agent can join in the reaction with pure form or the form of diluting in solvent.
The preferred solvent that is used for polyreaction is an aromatic solvent, typically toluene, dimethylbenzene or lightweight aromatic petroleum solvent.These solvents can be used with form fresh or that reclaim from technology.Solvent contains＜200ppm water usually, preferred＜100ppm water and most preferably＜50ppm water.Preferred solvent is an aromatic solvent.Usually, unreacted sylvic oil component reclaims as solvent by process quilt.Except recovered solvent, can use toluene, dimethylbenzene or aromatic petroleum solvent.These solvents can be used with form fresh or that reclaim from technology.Usually contain＜500ppm water preferred＜200ppm water and most preferably＜50ppm water in this solvent.Solvent can also be not polymerisable component in the raw material.
As for polymeric reaction condition, the first important variable is employed catalyst consumption.With the monomer weight is benchmark, and preferably the amount of using is 0.1wt%-30wt%.For the pure monomer resin, the preferred 0.1-15wt% of concentration, more preferably 0.5wt%-10wt% and most preferably 0.5wt%-8wt%.For C
5Monomer, the preferred 0.5-30wt% of concentration, more preferably 1wt%-20wt% and most preferably 3wt%-15wt%.For C
9Monomer, the preferred 0.5-30wt% of concentration, more preferably 1wt%-20wt% and most preferably 3wt%-15wt%.
The second important variable is a reaction sequence in the reaction, i.e. the order of combinations of reactants and mode.In a kind of reaction sequence, in monomer solution, add catalyzer incrementally, simultaneously control reaction temperature.Perhaps, in another reaction sequence, in the catalyst slurry in solvent, add monomer incrementally.For a series of catalyst contents and temperature of reaction, when in catalyst slurry, adding monomer, obtain lower basically softening temperature.Compare with the resin that adding catalyzer in monomer obtains, when adding monomer in catalyst slurry, the resin of acquisition has lower molecular weight and narrow polymolecularity (PD), i.e. Mw/Mn (measuring by size exclusion chromatography).
By the person's character of change carrier and the person's character and the consumption of promotor, catalyst system used in the present invention is the acidity of control catalyst better.This can control resin property, especially molecular weight and polymolecularity conversely better, and narrow polymolecularity is important, and it can guarantee the polymer-compatible in resin and the end-use.
The 3rd important variable is temperature of reaction.Can use the polymerization temperature between-50 ℃-150 ℃, yet preferred temperature is-20 ℃-100 ℃, most preferably 0 ℃-70 ℃.For pure monomer, preferred-50 ℃-100 ℃ of temperature, more preferably-20 ℃-75 ℃ and most preferably-10 ℃-60 ℃.For C
5Monomer, temperature are between-50 ℃-100 ℃, more preferably-20 between ℃-75 ℃, most preferably-10 between ℃-70 ℃.For C
9Monomer, preferred 0 ℃-150 ℃ of temperature, more preferably 10 ℃-120 ℃, most preferably 20 ℃-110 ℃.Find that temperature has significant effects to resulting resin property.Preparation has the resin of higher molecular weight and high softening temperature under lower temperature of reaction.
Can various different reactors as continuously, intermittently, in semi-batch, fixed bed, fluidized-bed and the plug flow reactor with continuously, intermittently or the method for semi-batch carry out polymerization technique.For example, in continuous processing, the monomer solution catalyzer in the fixed bed of can flowing through, or monomer infeeds in the flow reactor with catalyst slurry.Preferred fixed bed reaction because along with raw material enters reaction bed, can be removed painted material by catalyst system, thereby can improve the color of resin, described raw material typically enters at the top of fixed bed, makes in the bottom, typically obtains to improve the resin of color in the bottom of fixed bed.
But separating catalyst termination reaction physically from product.Physical sepn can make reaction soln be neutral.And, can realize physical sepn by simple filtering or the mode by separation resin solution from the fixed catalytic bed.The result does not have residual acid functionality and catalyst residue in rosin products.
We find that catalyst system used in the present invention is durable and stable.They keep active for a long time, and this shows that industrial application is feasible.
After the preparation resin, can carry out hydrogenation subsequently to reduce painted and to improve colour stability.
Can use any already known processes hydrogenation resin of the present invention of catalytic hydrogenation hydrocarbon resin; That especially suitable is US5171793, US4629766, US5502104 and US4328090 and WO95/12623.Total hydrogen treatment condition is included in about 100 ℃-350 ℃ temperature range and 5 normal atmosphere (506kPa)-300atm (30390kPa) hydrogen, and for example, the pressure of 10-275atm (1013kPa-27579kPa) is reaction down.In one embodiment, temperature is in comprising the scope of 180 ℃ and 320 ℃, and pressure is in the scope that comprises 15195kPa and 20260kPa hydrogen.The hydrogen under standard conditions in (25 ℃, 1atm (101kPa) pressure) reactor and the volume ratio of raw material typically in the 20-200 scope, for colourless resin, preferred 100-200.
The suitable technology of another hydrogenation resin of the present invention is disclosed in EP0082726.EP0082726 discloses and has used the nickel-tungsten catalyst catalysis of load on gamma-aluminium oxide carrier or the technology of hot hydrogenated petroleum resin, and wherein hydrogen pressure is 1.47 * 10
7-1.96 * 10
7Pa and temperature are in 250-330 ℃ of scope.Hot hydrogenation is usually at 160 ℃-320 ℃ and 9.8 * 10
5-11.7 * 10
5Typically carry out 1.5-4 hour time period under the pressure of Pa.After the hydrogenation, but flashing reactor mixture and further Separation and Recovery hydrogenated resin.Can use vapor distillation to reduce oligopolymer, preferably be no more than 325 ℃ resin temperature.
In an embodiment preferred, contact pressure resin is to carry out hydrogenation in the presence of hydrogen and hydrogenation catalyst, wherein said hydrogenation catalyst is the typical metal compound of load on the fire-resistant matrix granule of porous typically, and the fire-resistant matrix granule of described porous has:
A) average maximum diffusion path length is less than or equal to 2 times of hydraulic radiuses;
B) volume distributed median in hole, wherein:
I) hole of diameter＞150000 dusts constituted cumulative volume about 2% more than;
Ii) the hole of diameter＞20000 dusts and＜150000 dusts constituted cumulative volume about 1% more than and
Iii) the hole of diameter＞2000 dusts and＜20000 dusts constituted cumulative volume about 12% more than and
C) cumulative volume in hole accounts for the 45%-86% of matrix granule cumulative volume.
In an especially preferred embodiment, catalyzer comprises nickel and/or the cobalt on one or more molybdenums, tungsten, aluminum oxide or silica supports.In a preferred embodiment, on the carrier consumption of nickel oxide and/or cobalt oxide in the 2-10wt% scope.The consumption of the oxide compound of tungsten or molybdenum is in the 5-25wt% scope on the carrier of preparation back.Preferably, catalyzer contains 4-7wt% nickel oxide and 18-22wt% Tungsten oxide 99.999.This technology and appropriate catalyst at length are disclosed among the WO98/22214.
In another embodiment preferred, can use in the United States Patent (USP) 4629766 disclosed technology and catalyzer to carry out hydrogenation.Especially, the preferred nickel-tungsten catalyst on gama-alumina.
Resin of the present invention can be combined to form tackiness agent with base polymer.Typical base polymer comprises ceridust, ethene and reaches one or more C of 50wt% most
3-C
20The product of alpha-olefin copolymer, polypropylene, propylene and the most nearly one or more ethene and/or the C of 50wt%
4-C
20(density is that 0.915-is less than 0.935g/cm for the product of alpha-olefin copolymer, polybutene, ethylene vinyl acetate copolymer, new LDPE (film grade)
3), LLDPE, (density is that 0.86-is less than 0.90g/cm to ultra-low density polyethylene
3), (density is that 0.90-is less than 0.915g/cm to very low density polyethylene
3), (density is that 0.935-is less than 0.945g/cm to medium-density polyethylene
3), (density is that 0.945-is less than 0.98g/cm to high density polyethylene(HDPE)
3), EMA, acrylic acid multipolymer, polymethylmethacrylate or by any other polymkeric substance of high-pressure free radical method polymeric, PVC, poly-1-butylene, complete same polybutene, elastomerics such as second-third rubber (EPR), sulfuration EPR, EPDM, elastomer block copolymer such as SBS (styrene-butadiene-styrene), SIS (styrene-isoprene-phenylethene), nylon, polycarbonate, the PET resin, crosslinked polyethylene, the multipolymer of ethene and vinyl alcohol (EVOH), the polymkeric substance of aromatic monomer such as polystyrene, iso-butylene and to the multipolymer of ring-alkylated styrenes, poly--1 ester, high molecular HDPE, lower molecular weight HDPE, common graft copolymer, the homopolymer of polyacrylonitrile or multipolymer, polyamide thermoplastic, polyacetal, polyvinylidene difluoride (PVDF) and other fluorizated elastomerics, polyethylene glycols, polyisobutene (PIB) or its mixture.
In a preferred embodiment, base polymer is selected from segmented copolymer, polyisoprene, isoprene-isobutylene rubber, ethylene vinyl acetate, ethylene methacrylate, amorphous polypropylene, propylene diene hydrocarbon monomer rubber, ethene and the C of vinylbenzene and isoprene or divinyl
3-C
20The multipolymer of alpha-olefin, propylene and ethene or C
4-C
20The multipolymer of alpha-olefin, metallocene PE, metallocene polypropylene, natural rubber, styrene butadiene ribber, iso-butylene and to the multipolymer of ring-alkylated styrenes.Especially preferred polymkeric substance is styrene-butadiene-styrene block copolymer, isoprene-isobutylene rubber, natural rubber and styrene butadiene rubbers.
In an especially preferred embodiment, base polymer is SIS (styrene-isoprene-phenylethene) segmented copolymer.In another especially preferred embodiment, the SIS segmented copolymer exists 10wt% or diblock still less, preferred 5wt% or still less.The base of optimum selection polymkeric substance is to be available commercially from DEXCO POLYMERS, the styrene isoprene styrene block copolymer (SIS) of commodity VECTOR by name.
In another embodiment preferred, base polymer is to use the polymkeric substance of metallocene catalyst system preparation.Typically, use single-or two-cyclopentadienyl transition-metal catalyst, and with aikyiaiurnirsoxan beta and/or in solution, slurry, high pressure or gas phase non-coordinate anion active agent combination with preparation metallocene homopolymer or multipolymer.Catalyst system can be by load or can not be substituted or not be substituted by load and cyclopentadienyl rings.Titanium, zirconium and hafnium are preferred transition metal.Some Industrial products with this catalyzer/activating mixtures preparation can be at Baytown, and Texas is available commercially from Exxon Chemical Company, and its commodity are called EXCEED
TMAnd EXACT
TMAnd available from the polymkeric substance of Dow Chemical Company, its commodity are called ACHIEVE
TMAbout the more information of the method for preparing these metallocene homopolymer and multipolymer and catalyzer/activator referring to WO94/26816; WO94/03506; EPA277003; EPA277004; US5153157; US5198401; US5240894; US5017714; CA1268753; US5324800; EPA129368; US5264405; EPA520732; WO9200333; US5096867; US5507475; EPA426637; EPA573403; EPA520732; EPA495375; EPA500944; EPA570982; WO91/09882; WO94/03506 and US5055438.
The composition Tile Width index (CDBI) preferred 50% or more of the above-mentioned multipolymer of metallocene-prepared preferably is higher than 60%, even more preferably is higher than 70%.In one embodiment, CDBI is higher than 80%, even more preferably is higher than 90%, even more preferably is higher than 95%.In another especially preferred embodiment, multipolymer is a polyethylene, and its CDBI is between 60-85%, even more preferably between 65-85%.
Forming Tile Width index (CDBI) is to measure the distribution of monomer component in the polymer chain and apply for that by PCT disclosed step is measured among the WO93/03093 (on February 18th, 1993 is open).When measuring CDBI, weight-average molecular weight (Mw) is lower than 15000 part and ignores.
In adhesive formula, be benchmark with per 100 parts of base polymers, there is 1-200 part resin in the mixture.In a preferred embodiment, be benchmark with per 100 parts of polymkeric substance, there is 25-200 part resin in the mixture.In another embodiment, be benchmark with per 100 parts of polymkeric substance, the preferable range of resin is 80-120 part.
Also can contain additive well known in the art such as anti, static inhibitor, oxidation inhibitor, UV stablizer, neutralizing agent, lubricant, tensio-active agent and/or nucleator in the adhesive formula.Preferred additives comprises silicon-dioxide, titanium dioxide, polydimethylsiloxane, talcum, dyestuff, paraffin, calcium stearate, carbon black and granulated glass sphere.
Resin can form and enter in pressure sensitive adhesive, hotmelt or the contact adhesive, and is used in as adhesive tape, label, paper dipping, the hotmelt that comprises wood working, packing, bookbinding or processing, sealing agent, rubber compound, pipeline packing, underlayment, in the application of pressure sensitive adhesive, road sign or Tyre structure and polymeric additive and so on.
In an especially preferred embodiment, resin is fitted in the pressure sensitive adhesive applications.This contact adhesive composition can be applied to any routine backing layer such as paper, aluminium foil, polymer flake, release liner (release liners), weave or the nonwoven lining material comes Production Example such as gummed tape.
Resin of the present invention also can be used as properties-correcting agent and be used as Texturized again dose (re-texturising agent) of dry-cleaning in tackiness agent, sealing agent, printing-ink, supercoat, plastics, polymeric film, Application in Building such as road sign, earth material, paper additive.
The application that these petroleum resin are even more important is to be used as tackifier in adhesive composition such as solvent-based adhesive, hotmelt and pressure sensitive adhesive.In these adhesive compositions, petroleum resin serve as the tackifier of employed other polymkeric substance and rubber in the adhesive composition.The person's character of tackiness agent and specific application thereof are depended in the selection of polymkeric substance and/or rubber.For example, hotmelt is normally based on the multipolymer that contains ethene, particularly ethylene.Normally based on natural or synthetic rubber such as styrol copolymer rubber, solvent-based adhesive can be aqueous emulsion or organic solvent based adhesive to pressure sensitive adhesive, but considers environment reason, preferred Aquo System.The example of useful polymkeric substance is polyacrylic ester and polymethacrylate emulsion in these aqueous binder systems.
Because the acid position is the intrinsic part of catalyzer, so resin product or solvent are very little by the degree that catalyst residue pollutes.As a result, catalyzer does not give hydrocarbon resin unwanted color.If use pure styrene-based monomers, then resulting resin can be colourless.And resin does not have fluoride impurities basically.
Catalyzer used in the present invention is durable, thinks that its life cycle is long and can be reproduced or reclaim usually, thereby reduce the expensive catalysts waste treatment the biglyyest.By contrast, the normally single catalyst for application of the Lewis acid of load not.
And, with the lewis acid catalyst such as the BF of the not load of routine
3And AlCl
3Compare, catalyzer of the present invention is not dangerous.In a single day catalyzer of the present invention is exposed in the moisture, does not produce corrosion or dangerous liquid or gaseous acid usually.
Set forth the present invention by following embodiment:
Embodiment 1
Use following raw materials according to form in this embodiment:
Raw material A-
Aliphatic series C
5-C
6Raw material, wherein contain:
8.4% stable hydrocarbon
40.8% alkene
49.0% diolefine
Raw material B-
Aliphatic series C
5-C
6Raw material, wherein contain:
32.6% saturates
63.0% alkene
3.7% diolefine
Raw material C-
Aromatics C
8-C
9Raw material, wherein contain:
33.2% can not polymkeric substance
45.57% polymerizable thing
17.88% part polymerizable thing
The remainder of raw material is not determined.
Employed catalyzer prepares according to the following step:
With the 10gms surface-area is 310m
2g
-1Mesoporous silica (K100-Merck) 300 ℃ dry 24 hours down, under 20 ℃, nitrogen atmosphere, stir, use 4.2gms BF
3(H
2O)
2(Aldrich 96%) dilutes the mixture that obtains in 100ml ethanol promotor, stirred catalyst slurry 2 hours, and is slowly dry to remove unnecessary ethanol, about 50ml on rotatory evaporator under 50 ℃ then.
Then in the 2L Kimble flask of being furnished with 500ml dropping funnel, catalyzer dropping funnel, condenser, thermopair, overhead stirrer and nitrogen conduit (so that inert atmosphere to be provided), carry out polymerization.
The 35ml dry toluene is put into reactor with the catalyzer of the above-mentioned preparation of 14g.Stirred reactor under 600rpm is with 900ml raw material and the saturated C of 20wt%
5/ C
6Feedstream parallel feeding 1.5 hours, wherein said 900ml raw material comprises
28% raw material A
16% raw material B
36% raw material C
Be used under the existence of 40g 4 dust molecular sieve absorbents, in the prior dried feed of 24 hours molecular sieve of 300 ℃ of dryings.
Carry out this thermopositive reaction at ambient temperature.
1.5 after hour, filter, add the mode termination reaction that 120mlCorexit 8380,60ml ammonia come quencher then.
Obtain resin by stripping then.
The Mn of resin is 580, and Mw is 1380, Mz be 7400 and softening temperature be 81 ℃.
Prepare the pressure sensitive adhesion agent formulation by 90 parts by weight resin are mixed with 100 parts of solution, the 10%lvory Coast natural rubber of wherein said solution Mooney50 is dissolved in 90 parts of DSP, 9 parts of toluene and 1 part of methyl alcohol and forms.
Following table has been listed the performance of pressure sensitive adhesive, wherein
Every square metre coating weight is 20-22g;
Measure the bounding force that 1800 times are peeled off on steel according to AFERA testing method 4001;
According to the annular viscosity of FINAT testing method 9 measurements on steel;
Measure spherical viscosity according to PSTC6;
Measure in the shearing on the steel and on cardboard according to PSTC7.
Resin productive rate of the present invention is 16%, and with identical raw material, the AlCl of working load
3The resulting productive rate of catalytic resin is 5%.Resin of the present invention contains 42.8% aromatic substance, and AlCl
3Resin is 31.5%, and the softening temperature of resin of the present invention is 81 ℃, and AlCl
3Resin is 77 ℃, and the Mn of resin of the present invention is 580, and AlCl
3Resin is 820.The bond properties of resin of the present invention is made comparisons with similar tackiness agent, and wherein the latter contains useful identical raw material, utilizes the AlCl of load
3The resulting resin of catalyzer.
Pressure sensitive adhesive
| Resin | Embodiments of the invention | The AlCl of load 3Catalytic resin |
| 180 ° of bounding forces of peeling off (N/cm) (steel) | ?1.92 | ????2.08 |
| Annular viscosity (N/25mm) (steel) under the room temperature | ?5.8 | ????6.2 |
| Spherical viscosity (cm) | ?4.5 | ????2.0 |
| Shearing 12.5mm*25mm-1kg (hrs) under the room temperature on steel | ?＞100 ?＞100 ?＞100 | ????17.8cf ????21.8cf ????23.9cf |
| Shearing 12.5mm*25mm-1kg (hrs) (bookbinding cardboard) under the room temperature on cardboard | ?35.52cf ?32.72cf ?39.18cf ?50.03cf | ????9.03cf ????10.46cf ????7.91cf |
Cf refers to can't be bonding
Embodiment 2
Preparation catalyzer as described below in this embodiment:
With 4.2gms BF
3(H
2O)
2Join in the 100ml dehydrated alcohol promotor, add 10g silicon-dioxide (K100,300m
2g
-1, drying is 24 hours under 300 ℃), stirred slurry 2 hours down at 20 ℃, to transfer to then in the rotatory evaporator, unnecessary there ethanol evaporates down at 50 ℃, up to the catalyzer complete drying.
Carry out various polymerizations according to following step.With the nitrogen gas stream cleaning reaction device of 50ml/min, then with the 4mmolg of 17ml dry toluene with different amounts
-1BF
3(H
2O)
2/ SiO
2/ EtOH catalyzer (preparation as mentioned above) adds in the reactor together, and stirs with the preparation slurry.In 90 minutes, slowly add 450ml C then
8-C
9Aromatic raw material (with 10g 4 dust molecular sieve pre-treatment 24 hours).
Use 2.5,5 and the resulting following table 2 that the results are shown in of 10g catalyzer, therefrom can find out, catalytic amount is increased to 5g from 2.5, and prepared resin productive rate becomes about 2 times, also keeps suitable resin property simultaneously.Yet the amount that increases catalyzer causes the resin productive rate of 28 ° of much higher heat releases and 28% to 10g.
Table 2
| Catalyst consumption gms | Productive rate (%) | Heat release | Gardner color |
| ?????2.5 | ????2％ | ????3° | ????16 |
| ?????5.0 | ????4.5％ | ????4° | ????13 |
| ?????10.0 | ????28％ | ????28° | ????8 |
Embodiment 3
In this embodiment, use the 5gms catalyzer, repeat the method for embodiment 2.In an experiment, omit the drying of raw material.
The result is as follows:
| Raw material | Productive rate (%) | Heat release | Gardner color |
| Exsiccant | ??4.5％ | ??4° | ????13 |
| Wet | ??7.5％ | ??4° | ????9 |
Embodiment 4
This embodiment uses exsiccant raw material and the polymerizing condition of embodiment 2, relatively working load and unsupported (homogeneous phase) catalyzer.
The result is as follows:
| Productive rate (%) | Heat release | Gardner color | ???Mn | ????Mw | |
| 5g catalyzer of the present invention | ????4.5％ | ????4° | ????13 | ???510 | ????1670 |
| 20mmol homogeneous phase BF 3(H 2O) 2 | ????17％ | ????30° | ????8 | ???370 | ????760 |
Homogeneous phase BF
3Use cause much bigger heat release and higher resin productive rate, but with compare with resulting those resins of heterogeneous catalyst, material property worsens.
Embodiment 5
Except only using raw material C, repeat the method for embodiment 1, the result, the polymerizable thing is aromatic substance entirely in the raw material, obtains the conversion of unsaturates 100%.
Embodiment 6
By ten sequential polymerisation reactions, be evaluated at the stability of the boron trifluoride/ethanol complex catalyzer of load on the silicon-dioxide, wherein all in reactor, add embodiment 5 employed polymerizing catalysts and all aromatic raw materials in each polyreaction.
In case behind the temperature-stable of reactor, add next section raw material and catalyzer in each polyreaction.
In the 8th polyreaction in this sequence, do not add catalyzer, in the 9th polyreaction, do not add raw material.The results are shown in following table:
| Test | ?M SiO2，g | The volume of C9 raw material | ??t，min | ????ΔT |
| ????1 | ???0.344 | ?????15 | ????20 | ????4.4 |
| ????2 | ???0.336 | ?????15 | ????20 | ????5.4 |
| ????3 | ???0.335 | ?????15 | ????24 | ????5.6 |
| ????4 | ???0.337 | ?????15 | ????20 | ????3.4 |
| ????5 | ???0.326 | ?????15 | ????19 | ????4.8 |
| ????6 | ???0.345 | ?????15 | ????16 | ????3.7 |
| ????7 | ???0.334 | ?????15 | ????13 | ????3.2 |
| ????8 | ?????- | ?????15 | ????10 | ????2.2 |
| ????9 | ???0.338 | ??????- | ????15 | ?????- |
| ????10 | ???0.344 | ?????15 | ????11 | ????1.7 |
Δ T shows the activity when reacting generation, polymerization and shows that this catalyzer is durable and stable.Test the stability that adds raw material in 8 but do not add reaction proof catalyzer under reaction conditions of catalyzer.Add catalyzer in the test 9 but do not add raw material and prove that then all polymerisable components react in test 8.
Claims (19)
1. by polymerization C
4-C
6And/or C
8-C
9The method of unsaturated hydro carbons feedstock production petroleum resin wherein, makes raw material contact with catalyzer under polymerizing condition, and described catalyzer comprises the boron trifluoride/promotor complex compound of load.
2. the process of claim 1 wherein that the molecular formula of boron trifluoride/promotor complex compound is BF
3HX, wherein HX is a complexing agent.
3. the process of claim 1 wherein that the Pka of HX is 2.0～-4.5.
4. the method for aforementioned arbitrary claim, wherein catalyzer shows Louis and broensted acidity.
5. the method for aforementioned arbitrary claim, wherein promotor is an organism.
6. the method for aforementioned arbitrary claim, wherein promotor is an alcohol.
7. the method for claim 6, wherein Chun molecular formula is ROH, wherein R is methyl, ethyl, propyl group or butyl.
8. any one method of claim 1-5, wherein promotor is a carboxylic acid.
9. the method for claim 8, wherein acid is acetate.
10. the method for aforementioned arbitrary claim, wherein, with boron trifluoride/promotor complex compound reaction before, carrier contains surface hydroxyl and/or contains the oxygen base.
11. the method for aforementioned arbitrary claim, wherein carrier is a silicon-dioxide.
12. the method for aforementioned arbitrary claim, wherein raw material is to comprise C
8-C
9Polymerizable thing and aromatics petroleum that can not polymkeric substance.
13. the method for aforementioned arbitrary claim, wherein raw material is C
5-C
6Raw material and C
8-C
9The mixture of raw material.
14. the method for aforementioned arbitrary claim, wherein catalyzer reuses.
15. any one prepared petroleum resin of method of claim 1-14.
16. the petroleum resin of claim 15, described petroleum resin are hydrogenated.
17. a binder formulation is comprising the resin of natural or synthetic polymer and claim 16.
18. the pressure sensitive adhesive of claim 17, wherein natural polymer is a natural rubber.
19. any one prepared resin of claim 1-14 is as the purposes of component in tackiness agent, sealing agent, road sign material, paper additive, printing ink and polymer composition.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GBGB9916855.1A GB9916855D0 (en) | 1999-07-20 | 1999-07-20 | Petroleum resins and their production with BF3 catalyst |
| GB9916855.1 | 1999-07-20 | ||
| US15366399P | 1999-09-14 | 1999-09-14 | |
| US60/153663 | 1999-09-14 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1451021A true CN1451021A (en) | 2003-10-22 |
Family
ID=26315776
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN00810555A Pending CN1451021A (en) | 1999-07-20 | 2000-07-19 | Petroleum resins and thir production with BF3 catalyst |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP1208125A1 (en) |
| KR (1) | KR20020015381A (en) |
| CN (1) | CN1451021A (en) |
| AU (1) | AU6827500A (en) |
| BR (1) | BR0013176A (en) |
| MX (1) | MXPA02000651A (en) |
| WO (1) | WO2001005857A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101412786B (en) * | 2007-10-18 | 2011-04-06 | 中国石化上海石油化工股份有限公司 | Method for utilizing waste liquid from cyclopentadiene production using C9 distillate |
| CN111790443A (en) * | 2020-07-17 | 2020-10-20 | 万华化学集团股份有限公司 | Supported catalyst and preparation method and application thereof |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101589271B1 (en) * | 2010-03-11 | 2016-01-27 | 페트로케미칼 서플라이, 아이엔씨. | Activated inorganic metal oxides |
| US8829105B2 (en) | 2012-01-18 | 2014-09-09 | Eastman Chemical Company | Low molecular weight polystyrene resin and methods of making and using the same |
| CN103319659B (en) * | 2012-03-23 | 2015-09-09 | 天津德兰玮诚科技有限公司 | Multicomponent copolymer petroleum resin and preparation method thereof |
| CN103319660B (en) * | 2012-03-23 | 2015-07-01 | 天津鲁华化工有限公司 | Hydrogenated multicomponent copolymerized petroleum resin and preparation method thereof |
| MX2014015459A (en) | 2012-06-18 | 2015-07-14 | Petrochemical Supply Inc | Polyisobutylene composition having internal vinylidene and process for preparing the polyisobutylene polymer composition. |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4394296A (en) * | 1979-12-17 | 1983-07-19 | Gulf Research & Development Company | Boron trifluoride-water-silica catalyst |
| GB2169614A (en) * | 1984-12-31 | 1986-07-16 | Mobil Oil Corp | Producing alpha-olefins and their conversion into lubricants |
| US5268520A (en) * | 1987-07-30 | 1993-12-07 | The Lubrizol Corporation | Lower alkene polymers |
| JP2944229B2 (en) * | 1991-02-01 | 1999-08-30 | 出光石油化学株式会社 | Method for producing olefin oligomer |
| EP0936229B1 (en) * | 1998-02-12 | 2004-04-28 | Eastman Chemical Resins, Inc. | Process for the preparation of aromatic modified aliphatic hydrocarbon resins giving an excellent balance between tack and shear properties |
| GB9819456D0 (en) * | 1998-09-07 | 1998-10-28 | Univ York | Synthesis of a new supported bf-complex solid acid catalyst |
-
2000
- 2000-07-19 BR BR0013176-8A patent/BR0013176A/en not_active IP Right Cessation
- 2000-07-19 KR KR1020027000756A patent/KR20020015381A/en not_active Application Discontinuation
- 2000-07-19 WO PCT/EP2000/007084 patent/WO2001005857A1/en not_active Application Discontinuation
- 2000-07-19 AU AU68275/00A patent/AU6827500A/en not_active Abandoned
- 2000-07-19 CN CN00810555A patent/CN1451021A/en active Pending
- 2000-07-19 EP EP00956267A patent/EP1208125A1/en not_active Withdrawn
- 2000-07-19 MX MXPA02000651A patent/MXPA02000651A/en unknown
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101412786B (en) * | 2007-10-18 | 2011-04-06 | 中国石化上海石油化工股份有限公司 | Method for utilizing waste liquid from cyclopentadiene production using C9 distillate |
| CN111790443A (en) * | 2020-07-17 | 2020-10-20 | 万华化学集团股份有限公司 | Supported catalyst and preparation method and application thereof |
| CN111790443B (en) * | 2020-07-17 | 2022-11-04 | 万华化学集团股份有限公司 | Supported catalyst and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2001005857A1 (en) | 2001-01-25 |
| EP1208125A1 (en) | 2002-05-29 |
| AU6827500A (en) | 2001-02-05 |
| KR20020015381A (en) | 2002-02-27 |
| MXPA02000651A (en) | 2002-07-02 |
| BR0013176A (en) | 2002-04-02 |
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