CN103881027A - Synthetic method for piperylene petroleum resin - Google Patents
Synthetic method for piperylene petroleum resin Download PDFInfo
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- CN103881027A CN103881027A CN201210578592.6A CN201210578592A CN103881027A CN 103881027 A CN103881027 A CN 103881027A CN 201210578592 A CN201210578592 A CN 201210578592A CN 103881027 A CN103881027 A CN 103881027A
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- pentadiene
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Abstract
The invention discloses a synthetic method for piperylene petroleum resin. Piperylene, monoolefine and isoprene with a weight ratio of 1:(0.1-1.0):(0.1-0.5) are taken as raw materials of a copolymerization reaction; under the effect of a catalyst, at 40-70 DEG C, under the condition of oxygen-free environment, a cationic polymerization reaction is performed for synthesize resin by taking inert aliphatic hydrocarbon as a solvent. Based on different application fields of piperylene petroleum resin, product indexes such as molecular weight, molecular weight distribution, softening point and the like are controlled by regulating the weight ratio of added monoolefine and isoprene, the weight ratio of the added solvent, polymerization reaction temperature and other conditions. Piperylene petroleum resin prepared according to the synthetic method possesses good performances about thickening property, oxidation stability, compatibility and the like, and is capable of satisfies usage requirements in the application fields of rubber, paint, printing ink, papermaking and the like.
Description
Technical field
The present invention relates to a kind of method of manufacture high-grade pentadiene petroleum resin, belong to macromolecular material and production automation technical field.
Background technology
M-pentadiene petro-resin is aliphatics C
5petroleum resin, its number-average molecular weight is in 300～3000 scopes.The main chain link of such petroleum resin is aliphatic hydrocarbon structure, has that acid number is low, compatibility good, a characteristic such as good, the water-fast and resistance to ethanol of binding property and chemical-resistant resistance.
With alicyclic C
5petroleum resin and C
5and C
9the copolymer resins of cut etc. is compared, aliphatics C
5petroleum resin have better tackifying, thermostability and more shallow color and luster, thereby have better application prospect in adhesive industry such as pressure sensitive adhesives, are also widely used in the industries such as rubber, coating, ink and papermaking.In addition aliphatics C,
5petroleum resin can also be applied to new field by the further modification of grafting.
As Chinese patent 00115445.1, a kind of preparation method of C 5 monoolefin modified m-pentadiene petro-resin is disclosed.Separate by carbon five the m-pentadiene enriched material A obtaining, wherein m-pentadiene percentage concentration is 60～80%, and carbon five separates the monoolefine B obtaining, wherein the weight percent concentration of isopentene is 10～30%, the feed ratio of material A and material B is 1: (0.1～1) (weight ratio), under the existence of tri-chlorination two aluminium, polymerization obtains m-pentadiene petro-resin.
And for example Chinese patent 200610030765.5, a kind of high-grade petroleum resin production technique is disclosed, comprise a kind of copolyreaction stock liquid of preparation, making its carbon pentaene hydrocarbon content is 80～92%, wherein being rich in diolefin fractions consisting (wt%) is: diolefin 45～75%, wherein m-pentadiene 40～95%, monoene, alkane are 54～24%, monoolefine is first amylene, wherein 2-methyl-1-butene alkene and 2-methyl-2-butene total amount > 20%, all the other alkene total amount < 40%.
In above public technology, by monoolefin modified m-pentadiene petro-resin, its thickening property is promoted to some extent, but monoolefin modified when its molecular weight is diminished, its cohesive strength also diminishes, and when for some field, easily adheres to processor; If while keeping higher molecular weight, product performance are variation again.And, when for the purposes such as rubber tackifier, pressure sensitive adhesive, need to improve with styrene block copolymer, natural rubber and various elastomeric consistency.
Therefore, how, in promoting m-pentadiene petro-resin tackifying, guaranteeing the performances such as its stability, consistency, is the problem of needing at present solution badly.
Summary of the invention
The synthetic method of pentadiene resin of the present invention, according to the difference of m-pentadiene petro-resin Application Areas, by regulate the monoolefine that adds and isoprene part by weight, add the condition such as part by weight, polymeric reaction temperature of solvent to control the product indexs such as the molecular weight of generated m-pentadiene petro-resin and distribution, softening temperature, its object is to make m-pentadiene petro-resin to possess the superperformance of the aspects such as tackifying, oxidative stability and consistency simultaneously, to meet the service requirements of the Application Areass such as rubber, coating, ink and papermaking.
For achieving the above object, the synthetic method of described pentadiene resin comprises:
By weight proportion 1: (0.1-1.0): (0.1-0.5) m-pentadiene, monoolefine, isoprene are fed intake and make copolyreaction raw material;
Under catalyst action, taking inertia aliphatic hydrocarbon as solvent, under 40-70 DEG C of temperature, oxygen-free environment condition, carry out cationic polymerization, prepare resin to synthesize.
As above-mentioned general planning, the most active with m-pentadiene character in copolyreaction raw material, the higher speed of reaction of m-pentadiene concentration is faster.
Monoolefine mainly as chain transfer catalyst, when reducing the generation of gel, can also lower molecular resin amount in copolyreaction raw material, reaches the object of modification.But along with increasing of consumption, softening temperature is also along with decline.
Isoprene also can with m-pentadiene and monoolefine copolymerization, in isoprene molecule, contain conjugated double bond, on two keys, adopt sp3 hydridization, methyl is not in end position, and steric hindrance is less, when two keys are subject to attack, more easily fracture, easily polymerization reaction take place, reacts active compared with m-pentadiene, in the time of cationoid polymerisation, moment more easily generates macromolecular structure, and therefore, isoprene is not in affecting resin property, can increase molecular weight, improve the softening temperature of resin; And in resin, introduced polyisoprene segment, make itself and the polymkeric substance such as styrene block copolymer (as SIS, SBS, SEBS), natural rubber and various synthetic rubber there is good consistency.
This programme is done to further optimization, and in reaction raw materials, described monoolefine is to contain a kind of of 4-9 carbon atom or the mixture of several monoolefines wherein.
This programme is done to further optimization, and described catalyzer is one or more in aluminum chloride, boron trifluoride, alkyl aluminum halide.
If use more catalyzer, neutralization washing will produce a large amount of waste water, has both increased cost, can directly affect again product form and aspect; If but use very few catalyzer, comonomer can not fully react again.Therefore, the consumption of described catalyzer is further optimized for the 0.5-4% (by weight proportion) into copolyreaction raw material.
This programme is done to further optimization, and described solvent is at least one in saturated straight chain alkane, branched paraffin, naphthenic hydrocarbon and the isomers thereof that comprises 5-12 carbon atom.
This programme is done to further optimization, and described solvent load is the 20-60% (by weight proportion) of copolyreaction raw material.
Described synthetic method comprises following operation steps:
(1) preparation copolyreaction raw material
Starting monomer m-pentadiene, monoolefine, isoprene distill to remove stopper, autopolymer, and the starting monomer after distillation adds molecular sieve and Seal and preservation is for subsequent use at low temperatures;
By m-pentadiene, monoolefine, isoprene by weight proportion 1: (0.1-1.0): (0.1-0.5) after mixing, add constant pressure funnel with syringe;
(2) prepare solvent
First inertia aliphatic hydrocarbon is distilled to remove stopper and autopolymer, more also Seal and preservation is for subsequent use at low temperatures to add molecular sieve;
(3) preparation catalyzer
In the reactor that adds nitrogen protection, add aluminum chloride, boron trifluoride or alkyl aluminum halide, or the mixture of this type of material;
Add solvent, under, 40-45 DEG C temperature environment anhydrous in anaerobic, stir to make polymerizing catalyst;
(4) polyreaction
Stir while to dropwise reaction raw material in reactor, drip and finish rear continuation and under 40-70 DEG C of temperature environment, be incubated processing;
Whole polyreaction adopts nitrogen to carry out anaerobic protection all the time;
(5) post-polymerization treatment
After copolyreaction, in reactor, add alkali lye to remove unreacted catalyzer;
Stir after static layering, then add the saturated common salt aqueous solution to wash polymer fluid in organic phase, until the pH value of water lotion is neutral;
Oil phase is proceeded in another reactor, process to remove solvent and unreacted copolyreaction raw material wherein by distillation;
Finally under the temperature environment of 250-300 DEG C, carry out vacuum distilling to slough residual solvent and oligopolymer, cooling after with preparation form pentadiene resin.
In sum, the present invention has the following advantages and beneficial effect:
1, its softening temperature of prepared pentadiene resin is between 90-130 DEG C, under the constant condition of thickening property, improved greatly stripping strength and cohesive strength, avoids the adhesivity to processor.
2, prepared pentadiene resin molecular weight can free adjustment, there is good consistency with polymkeric substance such as styrene block copolymer (as SIS, SBS, SEBS), natural rubber and various synthetic rubber, thereby can meet the service requirements of the Application Areass such as rubber, coating, ink and papermaking.
Embodiment
Embodiment 1, the synthetic method of described pentadiene resin operates in the steps below:
(1) preparation copolyreaction raw material
Starting monomer m-pentadiene, 2-amylene, isoprene distill to remove stopper, autopolymer, and the starting monomer after distillation adds molecular sieve and Seal and preservation is for subsequent use at low temperatures;
After m-pentadiene, 2-amylene, isoprene are mixed for 1: 1.0: 0.1 by weight proportion, add constant pressure funnel with syringe;
(2) prepare solvent
First Skellysolve A is distilled to remove stopper and autopolymer, more also Seal and preservation is for subsequent use at low temperatures to add molecular sieve;
(3) preparation catalyzer
At one, Electromagnetic Heating agitator is housed, in three mouthfuls of glass reactors of thermometer and nitrogen protection, vacuumizes and inflated with nitrogen displacement protection, add 0.5g aluminum chloride, then to add the Skellysolve A of 12g be solvent; Under this anaerobic anhydrous condition, under 40～45 DEG C of temperature condition, stir and can obtain polymerizing catalyst;
(4) polyreaction
Heating while stirring; In the time that its temperature rises to 55 DEG C, start dropwise reaction stock liquid, control water-bath and make temperature of reaction be stabilized in 50-60 DEG C, after dropping finishes, continue insulation reaction 2 hours;
Whole polyreaction adopts nitrogen to carry out anaerobic protection all the time;
(5) post-polymerization treatment
After copolyreaction, add 5% aqueous sodium hydroxide solution termination reaction and remove unreacted catalyzer;
Stir after static layering, then add the saturated common salt aqueous solution to wash polymer fluid in organic phase, until the pH value of water lotion is neutral;
Oil phase is proceeded in another reactor, process to remove solvent and unreacted copolyreaction raw material wherein by distillation;
Finally under the temperature environment of 260 DEG C, carry out vacuum distilling to slough residual solvent and oligopolymer, obtain pentadiene resin, 98 DEG C of softening temperatures after cooling, Gardner's colourity is 4, weight-average molecular weight (Mw) is 2353, and its yield is 87.3%, good with natural rubber, SIS consistency.
Embodiment 2, adopts technique means and the method steps identical with embodiment 1, and difference part is wherein:
30 grams of preparation copolyreaction raw materials, within 1: 0.5: 0.5 by weight proportion, mix m-pentadiene, 2-methyl-2-butene, isoprene, catalyzer adopts 0.9 gram of aluminum chloride, 10 grams of solvent normal hexanes, obtain resin through copolyreaction, 110 DEG C of softening temperatures, Gardner's colourity is 5, weight-average molecular weight (Mw) is 3243, and its yield is 92.6%, good with natural rubber, SIS consistency.
Embodiment 3, adopts technique means and the method steps identical with embodiment 1, embodiment 2, and difference part is wherein:
30 grams of preparation copolyreaction raw materials, within 1: 0.2: 0.4 by weight proportion, mix m-pentadiene, 2-methyl-1-butene alkene, isoprene, catalyzer adopts 0.2 gram of diethyl aluminum chloride, 12 grams of solvent normal hexanes, obtain resin through copolyreaction, 105 DEG C of softening temperatures, Gardner's colourity is 4, weight-average molecular weight (Mw) is 3367, and its yield is 85.9%, good with natural rubber, SIS consistency.
The mensuration of above softening temperature is undertaken by ring and ball method standard, and the mensuration of colourity adopts Gardner color standard to measure; Relative molecular mass distributes and adopts gel chromatography.
Claims (7)
1. a synthetic method for pentadiene resin, is characterized in that: by weight proportion 1: (0.1-1.0): (0.1-0.5) m-pentadiene, monoolefine, isoprene are fed intake and make copolyreaction raw material; Under catalyst action, taking inertia aliphatic hydrocarbon as solvent, under 40-70 DEG C of temperature, oxygen-free environment condition, carry out cationic polymerization, prepare resin to synthesize.
2. the synthetic method of pentadiene resin according to claim 1, is characterized in that: described monoolefine is to contain a kind of of 4-9 carbon atom or the mixture of several monoolefines wherein.
3. the synthetic method of pentadiene resin according to claim 1, is characterized in that: described catalyzer is one or more the mixture in aluminum chloride, boron trifluoride, alkyl aluminum halide.
4. the synthetic method of pentadiene resin according to claim 1, is characterized in that: by weight proportion, catalyst levels is the 0.5-4% of copolyreaction raw material.
5. the synthetic method of pentadiene resin according to claim 1, is characterized in that: described solvent is at least one in saturated straight chain alkane, branched paraffin, naphthenic hydrocarbon and the isomers thereof that comprises 5-12 carbon atom.
6. the synthetic method of pentadiene resin according to claim 1, is characterized in that: by weight proportion, solvent load is the 20-60% of copolyreaction raw material.
7. according to the synthetic method of the pentadiene resin described in arbitrary claim in claim 1-6, it is characterized in that: the operation steps that realizes synthetic method is,
(1) preparation copolyreaction raw material
Starting monomer m-pentadiene, monoolefine, isoprene distill to remove stopper, autopolymer, and the starting monomer after distillation adds molecular sieve and Seal and preservation is for subsequent use at low temperatures;
By m-pentadiene, monoolefine, isoprene by weight proportion 1: (0.1-1.0): (0.1-0.5) after mixing, add constant pressure funnel with syringe;
(2) prepare solvent
First inertia aliphatic hydrocarbon is distilled to remove stopper and autopolymer, more also Seal and preservation is for subsequent use at low temperatures to add molecular sieve;
(3) preparation catalyzer
In the reactor that adds nitrogen protection, add aluminum chloride, boron trifluoride or alkyl aluminum halide, or the mixture of this type of material;
Add solvent, under, 40-45 DEG C temperature environment anhydrous in anaerobic, stir to make polymerizing catalyst;
(4) polyreaction
Stir while to dropwise reaction raw material in reactor, drip and finish rear continuation and under 40-70 DEG C of temperature environment, be incubated processing;
Whole polyreaction adopts nitrogen to carry out anaerobic protection all the time;
(5) post-polymerization treatment
After copolyreaction, in reactor, add alkali lye to remove unreacted catalyzer;
Stir after static layering, then add the saturated common salt aqueous solution to wash polymer fluid in organic phase, until the pH value of water lotion is neutral;
Oil phase is proceeded in another reactor, process to remove solvent and unreacted copolyreaction raw material wherein by distillation;
Finally under the temperature environment of 250-300 DEG C, carry out vacuum distilling to slough residual solvent and oligopolymer, cooling after with preparation form pentadiene resin.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108017759A (en) * | 2016-10-28 | 2018-05-11 | 中国石油化工股份有限公司 | A kind of modified pentadiene hydrogenated petroleum resin and preparation method thereof |
| CN109306036A (en) * | 2018-08-17 | 2019-02-05 | 惠州大亚湾伊科思新材料科技发展有限公司 | A kind of cold poly- production method of Petropols reducing gel |
| CN110627935A (en) * | 2018-06-25 | 2019-12-31 | 中国石化工程建设有限公司 | Purification device and purification method for poly alpha-olefin reaction product |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1131680A (en) * | 1995-03-23 | 1996-09-25 | 中国科学院成都有机化学研究所 | Manufacture method of fatty hydrocarbon petroleum resin |
| JP2002030245A (en) * | 2000-07-14 | 2002-01-31 | Mitsui Chemicals Inc | Resin composition for traffic paint |
| CN1563127A (en) * | 2004-03-23 | 2005-01-12 | 倪才国 | Method for preparing petroleum resin of piperyene |
| CN102816281A (en) * | 2012-09-03 | 2012-12-12 | 南京源港精细化工有限公司 | Method for preparing C5 petroleum resin for traffic paint |
-
2012
- 2012-12-19 CN CN201210578592.6A patent/CN103881027B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1131680A (en) * | 1995-03-23 | 1996-09-25 | 中国科学院成都有机化学研究所 | Manufacture method of fatty hydrocarbon petroleum resin |
| JP2002030245A (en) * | 2000-07-14 | 2002-01-31 | Mitsui Chemicals Inc | Resin composition for traffic paint |
| CN1563127A (en) * | 2004-03-23 | 2005-01-12 | 倪才国 | Method for preparing petroleum resin of piperyene |
| CN102816281A (en) * | 2012-09-03 | 2012-12-12 | 南京源港精细化工有限公司 | Method for preparing C5 petroleum resin for traffic paint |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108017759A (en) * | 2016-10-28 | 2018-05-11 | 中国石油化工股份有限公司 | A kind of modified pentadiene hydrogenated petroleum resin and preparation method thereof |
| CN108017759B (en) * | 2016-10-28 | 2021-06-01 | 中国石油化工股份有限公司 | Modified pentadiene hydrogenated petroleum resin and preparation method thereof |
| CN110627935A (en) * | 2018-06-25 | 2019-12-31 | 中国石化工程建设有限公司 | Purification device and purification method for poly alpha-olefin reaction product |
| CN110627935B (en) * | 2018-06-25 | 2022-05-24 | 中国石化工程建设有限公司 | Purification device and purification method for poly alpha-olefin reaction product |
| CN109306036A (en) * | 2018-08-17 | 2019-02-05 | 惠州大亚湾伊科思新材料科技发展有限公司 | A kind of cold poly- production method of Petropols reducing gel |
| CN109306036B (en) * | 2018-08-17 | 2021-02-26 | 惠州伊斯科新材料科技发展有限公司 | Cold polymerization production method of petroleum resin capable of reducing gel |
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