CN1036999C - Process for producing solid petroleum resin with light colour - Google Patents
Process for producing solid petroleum resin with light colour Download PDFInfo
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- CN1036999C CN1036999C CN94107042A CN94107042A CN1036999C CN 1036999 C CN1036999 C CN 1036999C CN 94107042 A CN94107042 A CN 94107042A CN 94107042 A CN94107042 A CN 94107042A CN 1036999 C CN1036999 C CN 1036999C
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- petroleum resin
- prepolymerization
- polyreaction
- temperature
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Abstract
The present invention discloses a method for producing light-chrominance C9 solid petroleum resin by residue distillate of heavy byproduct cracking. In the present invention, distillate of heavy byproduct cracking is treated by activated clay and then dehydrated by molecular sieves, maleic anhydride is added to carry out the prepolymerization under the condition of inert gas protection, the cationic polymerization is carried out for a product which is obtained from the prepolymerization under the condition of inert gas protection, and light-chrominance C9 petroleum resin is obtained. The chrominance of the product which is produced in the present invention is less than 3 DEG. When the method which is given by an implementary instance of the present invention is adopted, a solid of which the product chrominance is approximate to colorless and transparent is obtained.
Description
The present invention relates to the multipolymer of hydrocarbon and oil, as the manufacture method of petroleum resin, is the residue cut (C with heavy by-product cracked oil more exactly
8～C
11) petroleum resin of making raw material production light color degree (generally claim C
9Petroleum resin) method.
C
9Petroleum resin are the residue cut (C that tell from heavy by-product cracked oil behind the benzene,toluene,xylene
8～C
11) form through cationoid polymerisation.Many by two sections polymerization productions of its component employing in the existing production method, the colourity of its product is generally 11～14# (Fe-Co colorimetry, promptly the Gardner colorimetry is as follows), because the product colour difference is very restricted the application of product.Produce the method that light colour petroleum resin adopts shortening more in the prior art.
United States Patent (USP) 4,118,555 disclose a kind of C
9The manufacture method of petroleum resin, this method comprises is at first giving aggregation processing with cracking fraction (containing alkene and diolefin) under 10～60 ℃ in the presence of the atlapulgite, filter then and remove carclazyte, distill again that to obtain boiling range be 150～240 ℃ fraction, add weight ratio then and be 0.05 to t C
5, under-100～100 ℃, carrying out polymerization in the presence of the cationic catalyst again, to obtain product with better colourity quality.The technical measures of this patent reality are at the relatively poor C of colourity
9Add colourity C preferably in the hydrocarbon component
5Hydrocarbon give to divide, reaching the purpose of improving product colourity, and its effect and bad, from the content of this patent disclosure as can be known its colourity preferably also can only reach 8#, but also cause the increase of production cost.
German Patent Ger 2,856,335 disclose a kind of residue cut with heavy by-product cracked oil mixes with maleic anhydride, itaconic anhydride, citraconic anhydride and methylene-succinic acid, 50～250 ℃ of following prepolymerizations, through distilling to such an extent that cut is done raw material, carry out under the cationic catalyst effect that catalyzed polymerization, resistance are poly-, to obtain colourity be the method for the petroleum resin of 4# in underpressure distillation.From this patent as seen, its production cost is higher, but the colourity of its product is still undesirable, and adopts raw material and maleic anhydride, itaconic anhydride, citraconic anhydride and methylene-succinic acid mixed system to carry out prepolymerization in prepolymerization, and its production cost is increased.
The purpose of this invention is to provide a kind of the deficiencies in the prior art that overcome, can produce the solid C of light degree
9The method of resin.
Purpose of the present invention realizes with following measure:
The residue cut of heavy by-product cracked oil generally is C
8～C
11, handle with atlapulgite earlier, remove moisture with molecular sieve then; under protection of inert gas, add maleic anhydride through the raw material of aforementioned processing and state capable prepolymerization; prepolymerized temperature is 80～120 ℃, and the add-on of maleic anhydride is 2～5% (maleic anhydrides: raw material, weight ratio.As follows), prepolymer product is carried out polyreaction through add cationic catalyst after the underpressure distillation under protection of inert gas, and polyreaction described here and reaction of the prior art are basic identical, only are that the temperature of polyreaction is controlled at-5～25 ℃.It is poly-to add alkaline stopper resistance behind the sufficient reacting in product, and product obtains C again after removing catalyzer, washing, underpressure distillation
9Petroleum resin.
The also available following method of purpose of the present invention realizes:
When prepolymerization, temperature is controlled to be 90～110 ℃, and the add-on of maleic anhydride is 2.5～3.3%.
Temperature of reaction is controlled at-3～3 ℃ in the polyreaction, and the catalyzer that is added is the Fu Shi catalyzer, and its consumption is 0.2～0.5%.
Adopt method of the present invention to make C
9Petroleum resin; owing in advance raw material has been carried out physical decolorization; in reaction, control the condition of reaction simultaneously; particularly polymerization temperature is controlled at lower temperature; and in prepolymerization and polyreaction, adopt protection of inert gas; the component that causes colourity to deepen in the product is suppressed, and the colourity of its finished product has significant improvement than prior art.The particularly method production of recommending with the embodiment of the invention, its product are close to and are water white solid resin, and the colourity of actual measurement is 1#.Because product colourity of the present invention is good, is C
9Petroleum resin have been opened up wide application field.
Working condition of the present invention is to carry out at normal temperatures and pressures, and its production cost is far below the shortening method, and the condition control ratio prior art in the production will be easy to many.Again because the present invention has only adopted maleic anhydride when prepolymerization, so the present invention is also lower than the production cost of German patent.
Aggregation processing temperature range of the present invention is-5～30 ℃, is easier to realize in industrial production.
Several embodiments of the present invention below are provided:
Embodiment 1
To handle and the raw material that dewaters 100 grams add in the four-hole bottles through atlapulgite, and add the maleic anhydrides of 5 grams simultaneously, four-hole bottle places oil bath, and the control oil bath temperature is at 80 ℃, and stirring reaction is about four hours under nitrogen protection.Product carries out underpressure distillation, gets 88 gram cuts.Described cut adds catalyzer and carries out cationic polymerization under nitrogen protection, temperature of reaction is controlled at about-5 ℃, and it is poly-to react after two hours the ammoniacal liquor resistance that adds 0.1 mole, and product carries out underpressure distillation after being washed to neutrality, final water white solid C
9About 29 grams of petroleum resin.Its colourity＜1# after measured.
Embodiment 2
To handle and residue cut 100 grams of the heavy by-product cracked oil that dewaters add in the four-hole bottles through atlapulgite, and add the maleic anhydrides of 3 grams simultaneously, four-hole bottle places oil bath, and the control oil bath temperature is at 90 ℃, and stirring reaction is about four hours under nitrogen protection.Product is 110～150 ℃ at oil bath temperature, carries out underpressure distillation under the 2KPa condition, gets the cuts of 92 grams.Described cut adds Fu Shi catalyzer (BF under nitrogen protection
3Et
2O) 1 milliliter is carried out polyreaction, and temperature of reaction is-3 ℃, reacts the Ca (OH) that adds 0.5 gram after two hours
2Water suspension resistance is poly-, and product carries out underpressure distillation when being washed to neutrality, final water white solid C
9About 29 grams of petroleum resin.Its colourity＜1# after measured.
Embodiment 3
To handle and the raw material that dewaters 100 grams add in the four-hole bottles through atlapulgite, and add the maleic anhydrides of 2.5 grams simultaneously, four-hole bottle places oil bath, and the control oil bath temperature is at 100 ℃, and stirring reaction is about four hours under nitrogen protection.Product is 100～150 ℃ at oil bath temperature, carries out underpressure distillation under the 2KPa condition, gets the cuts of 90 grams.Described cut adds Fu Shi catalyzer (BF under nitrogen protection
3Et
2O) 1 milliliter is carried out polyreaction, and temperature of reaction is 0 ℃, reacts the Ca (OH) that adds 0.5 gram after two hours
2Water suspension resistance is poly-, and product carries out underpressure distillation when being washed to neutrality, final water white solid C
9About 30 grams of petroleum resin.Its colourity is 1# after measured.
Embodiment 4
To handle and the raw material that dewaters 100 grams add in the four-hole bottles through atlapulgite, and add the maleic anhydrides of 3.3 grams simultaneously, four-hole bottle places oil bath, and the control oil bath temperature is at 104 ℃, and stirring reaction is about four hours under nitrogen protection.Product is 100～147 ℃ at oil bath temperature, carries out underpressure distillation under the 2KPa condition, gets the cuts of 90 grams.Described cut adds Fu Shi catalyzer (BF under nitrogen protection
3Et
2O) 1 milliliter is carried out polyreaction, and temperature of reaction is 3 ℃, and it is poly-to react after two hours the ammoniacal liquor resistance that adds 0.1 mole, and product carries out underpressure distillation when being washed to neutrality, final water white solid C
9About 32 grams of petroleum resin.Its colourity＜1# after measured.
Embodiment 5
To handle and the raw material that dewaters 100 grams add in the four-hole bottles through atlapulgite, and add the maleic anhydrides of 2 grams simultaneously, four-hole bottle places oil bath, and the control oil bath temperature is at 120 ℃, and stirring reaction is about four hours under nitrogen protection.Product carries out underpressure distillation, gets 93 gram cuts.Described cut adds Fu Shi catalyzer (BF under nitrogen protection
3Et
2O) 1 milliliter is carried out polyreaction, and temperature of reaction is 25 ℃, reacts the ammoniacal liquor resistance that adds 0.1 mole after two hours and gathers, and product carries out underpressure distillation after being washed to neutrality, the final solid C that gets
9About 33 grams of petroleum resin.Its colourity 2～3# after measured.
Claims (5)
1, C
9The manufacture method of petroleum resin, the residue cut (C of heavy by-product cracked oil
8～C
11) prepolymerization under 80～120 ℃ of conditions earlier, and then carry out cationic polymerization, and fully adding in product alkaline stopper resistance in back is poly-for polyreaction, and product obtains C again after removing catalyzer, washing, underpressure distillation
9Petroleum resin; it is characterized in that described residue cut handles with atlapulgite earlier; remove moisture with molecular sieve then; the maleic anhydride that adds 2～5% (weight ratios) through the raw material of aforementioned processing; under the protection of inert gas condition, carry out prepolymerization; the prepolymerization product to cut, carries out polyreaction under-5～25 ℃ and protection of inert gas condition after underpressure distillation.
2, method according to claim 1, the add-on of maleic anhydride are 2.5～3.3% (weight ratios).
3, method according to claim 2, the temperature when it is characterized in that prepolymerization are 90～110 ℃.
4, according to claim 1 or 2 or 3 described methods, it is characterized in that the temperature of polyreaction is-3～3 ℃.
5, method according to claim 4 is characterized in that described catalyzer is the Fu Shi catalyzer, and its consumption is 0.2～0.5% (weight ratio).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94107042A CN1036999C (en) | 1994-06-10 | 1994-06-10 | Process for producing solid petroleum resin with light colour |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94107042A CN1036999C (en) | 1994-06-10 | 1994-06-10 | Process for producing solid petroleum resin with light colour |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1114324A CN1114324A (en) | 1996-01-03 |
| CN1036999C true CN1036999C (en) | 1998-01-14 |
Family
ID=5032780
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94107042A Expired - Fee Related CN1036999C (en) | 1994-06-10 | 1994-06-10 | Process for producing solid petroleum resin with light colour |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1036999C (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102382261B (en) * | 2011-08-22 | 2013-03-06 | 天津市兴源化工有限公司 | Preparation method for light-chroma aromatic petroleum resin |
| CN102690393B (en) * | 2012-05-04 | 2013-12-04 | 北京化工大学 | Copolymer containing functional group and prepared by C5 mixture and maleic anhydride, and preparation of copolymer |
| CN105949388B (en) * | 2016-05-23 | 2019-03-29 | 北京化工大学 | A kind of functional copolymer directly prepared by higher carbon number hydrocarbon class mixture and preparation method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1525098A (en) * | 1976-08-05 | 1978-09-20 | Euteco Spa | Process for the preparation of petroleum resins |
| DE2856335A1 (en) * | 1977-12-26 | 1979-06-28 | Mitsui Petrochemical Ind | METHOD FOR PRODUCING HYDROCARBON RESINS WITH IMPROVED COLOR AND THERMAL STABILITY |
-
1994
- 1994-06-10 CN CN94107042A patent/CN1036999C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1525098A (en) * | 1976-08-05 | 1978-09-20 | Euteco Spa | Process for the preparation of petroleum resins |
| US4118555A (en) * | 1976-08-05 | 1978-10-03 | Euteco, S.P.A. | Process for the preparation of petroleum resins |
| DE2856335A1 (en) * | 1977-12-26 | 1979-06-28 | Mitsui Petrochemical Ind | METHOD FOR PRODUCING HYDROCARBON RESINS WITH IMPROVED COLOR AND THERMAL STABILITY |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1114324A (en) | 1996-01-03 |
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