WO1988003538A1 - Heat polymerization process to produce broad spectrum hydrocarbon resins - Google Patents

Heat polymerization process to produce broad spectrum hydrocarbon resins Download PDF

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Publication number
WO1988003538A1
WO1988003538A1 PCT/US1987/002949 US8702949W WO8803538A1 WO 1988003538 A1 WO1988003538 A1 WO 1988003538A1 US 8702949 W US8702949 W US 8702949W WO 8803538 A1 WO8803538 A1 WO 8803538A1
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WO
WIPO (PCT)
Prior art keywords
feed stream
reaction zone
styrene
broad spectrum
hydrocarbon resins
Prior art date
Application number
PCT/US1987/002949
Other languages
French (fr)
Inventor
Darryl F. Manuel
Original Assignee
Manuel Darryl F
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Manuel Darryl F filed Critical Manuel Darryl F
Publication of WO1988003538A1 publication Critical patent/WO1988003538A1/en

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/24—Stationary reactors without moving elements inside
    • B01J19/2415—Tubular reactors
    • B01J19/242—Tubular reactors in series
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J3/00—Processes of utilising sub-atmospheric or super-atmospheric pressure to effect chemical or physical change of matter; Apparatus therefor
    • B01J3/04—Pressure vessels, e.g. autoclaves
    • B01J3/042—Pressure vessels, e.g. autoclaves in the form of a tube
    • 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
    • C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F12/02—Monomers containing only one unsaturated aliphatic radical
    • C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00051—Controlling the temperature
    • B01J2219/00054—Controlling or regulating the heat exchange system
    • B01J2219/00056—Controlling or regulating the heat exchange system involving measured parameters
    • B01J2219/00058—Temperature measurement
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00051—Controlling the temperature
    • B01J2219/00074—Controlling the temperature by indirect heating or cooling employing heat exchange fluids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00051—Controlling the temperature
    • B01J2219/00074—Controlling the temperature by indirect heating or cooling employing heat exchange fluids
    • B01J2219/00087—Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements outside the reactor
    • B01J2219/00094—Jackets

Definitions

  • the invention relates to a heat polymerization process to produce a broad spectrum hydrocarbon resins, and more particularly a process which is intended to replace processes currently in use which rely upon the reaction of Friedel Crafts Catalysts.
  • the present invention relates to a novel continuous process for polymerization of aromatic monomers containing vinyl linkages, such as styrene, indene, vinyl toluen and higher and/or more complex aroraatics, as well as cyclic dien polymers, such as dicyclopentadiene and methyl cyclopentadiene, as well as other complex aliphatic monomers containing residual double bonds.
  • aromatic monomers containing vinyl linkages such as styrene, indene, vinyl toluen and higher and/or more complex aroraatics
  • cyclic dien polymers such as dicyclopentadiene and methyl cyclopentadiene, as well as other complex aliphatic monomers containing residual double bonds.
  • the process of the present invention yields broad spectrum, hydrocarbon resins having excellent color charac ⁇ teristics which provide formulating advantages in adhesives, paints, coatings and construction chemicals.
  • a particular advantage of the product produced by the process of the present invention resides in the production of a more reproducable polymer, having a regular repeating pattern as compared with a more random type of polymer that is produced with process utilizing Friedel Crafts Catalysts. Also, the present process achieves superior yields, as well as providing the capability of holding viscosity and melt point of the resulting polymer within narrower ranges as compared with the Friedel Crafts processes.
  • the process of the present invention employs heat to generate free radicals, rather than relying upon Friedel Crafts Catalysts. While the present processes has operating temperatures in the range of 450°F to 600°F as compared with the lower Friedel Crafts processses temperatures, the higher operational temperatures for the present invention utilize the heat of polymerization to maintain the reaction temperatures.
  • the stream of reactants is pumped in the desired pressure range of 150 to 275 p.s.i. and lead through several passes of reaction section of piping in a continuous plug flow reactor in order that the reaction will proceed on a continuous basis.
  • static mixers are positioned in each length of piping to create or enhance turbulent flow to provide for faster reaction rates. Further ⁇ more, turbulence is promoted by the periodic use of reduced diameter piping in the continuous plug flow reactor sections to further increase velocity of fluid flow, thereby increasing mixing efficiency and reaction rates.
  • Yet another advantage of the present invention is that the present process does not require the expensive step of neutralization of catalysts as is the case in the Friedel Crafts processes.
  • the present processes gives higher resin yields. Also, the present process allows for the use of peroxide catalysts if desired.
  • Another feature of the present process is that it can be regarded as a continuous plug flow reactor system, and therefore yields the advantages of such a system. It will be clear that the present process can be used to produce other types of polymers that are polymerized by addition reactions.
  • aromatic streams such as aromatic, olefinic monomers, vinyl toluene, styrene. alphamethyl styrene, indene, coumarone, methyl coumarone, methyl indene and Cg- ⁇ . 2 alkyl aromatics.
  • the foregoing can be polymerized alone or in combinatio with any one or more of dicyclopentadiene, methydicyclopentadien and other complex alphatic hydrocarbons of the C5 to C20 fc YP e with residual active double bonds and other typical monomers which polymerize by addition reactions, such as acrylic and methacrylic mononers.
  • the continuous plug flow reactor of the present invention yields polymer with high conversion rates and free of residual impurities which are typical of acid polymerized polymers.
  • the foregoing together with the use of stainless steel equipment and small amounts of antioxidant yields a product of excellent color, generally in the superior range of 6 to 8 on the Gardner Scale.
  • Figure 1 is a block diagram showing the basic process of the present invention
  • Figure 2 is a view showing the various piping lengths comprising the reaction zone in a continuous plug flow reactor.
  • feed stream involved with the process of the present invention involves the bringing together of 9315 pounds of styrene, 10,586 pounds of dicyclopentadiene, 6714 pounds of mineral spirits (a diluent), 42 pounds of an antioxidant and 2 pounds of cumene hydroperoxide.
  • the aforesaid monomer blend is fed into a continuous plug flow reactor, such as shown in Figure 2.
  • the reaction proceeds at approximately 500°F and a pressure of about 200 p.s.i.
  • reaction mixture which yields Product 1 as shown in the tables to follow.
  • Product 2 is similar to Product 1, but its feed stream will be comprised of 20 to 25% by weight styrene, 20% by weight of a high aliphatic residual double bond material and the balance dicyclopentadiene, the same small amount of antioxidant and the same optional small amount of a peroxide catalyst.
  • the peroxide catalyst can be selected from various symmetrical and unsymmetrical peroxides as contained in British Patent No. 837,525, the disclosure of which is incorporated by reference. These included mono and di alkyl and aryl peroxides as exemplified by Bis (a,a-dimethylbenzyl) peroxide, as well as dicumyl peroxide and 2,5 dimethyl-2,5 di(t-butyl peroxy) hexane (sold under Trademarks Varox and Lupersol 101).
  • the Product 3 has a feed stream that is identical to Product 1 except Product 3 is 25% by weight styrene and 75% by weight cyclopentadiene.
  • Curing compounds will benefit from Product l's moisture resistance and Product Ill's quick flake off properties. All alkyd paints, will benefit from Product 2's aliphatic tolerance and quick dry. These three broad spectrum hydrocarbon resins excel in many applications. The following lists some of the mor traditional uses for these three products.
  • Product 1 is reducible in regular mineral spirits to 15-35% with a slight haze at room temperature. It may form a slight precipitate at cold temperatures which will dissolve on warming.
  • Product 2 has excellent solubility being soluble in Rule 66 Mineral Spirits to 12%.
  • Product 3 is reducible in regular mineral spirits to 14% and is clear at room temperature although there is some possibility of forming a haze and slight precipitation at cool temperatures.
  • Adhesives 176.170 Components of paper and paperboard in contact with Aqueous and fatty foods.
  • the process of the present invention involves bringing together in a feed stream, a styrene monomer, dicylopentadiene, mineral spirits, an antioxidant and optionally a peroxide, followed by heating the feed stream in a reaction zone at a temperature range of from 450°F to ⁇ 00°F and at a pressure of 150 p.s.i. to 175 p.s.i., while moving the feed stream at a rate of from 2,400 to 5,000 pounds per hour through the reaction zone constituting a continuous plug flow reactor, and removing the resultant polymer from the reaction zone.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

A heat polymerization process to produce broad spectrum hydrocarbon resins involving bringing together in a feed stream, a double bond containing material such as styrene; mineral spirits, and an antioxidant, heating the feed stream in a reaction zone at a temperature range of from 450oF to 600o F and at a pressure range of 150 to 275 p.s.i. while moving the feed stream in a plug flow reactor at a rate of from 2400-5000 pounds per hour through the reaction zone, and removing the resultant polymer from the reaction zone. The double bond containing a material is styrene. In an alternative form, dicyclopentadiene is also added to the feed stream. Also, a peroxide catalyst may be used.

Description

HEAT POLYMERIZATION PROCESS TO PRODUCE BROAD SPECTRUM HYDROCARBON RESINS
Field of the Invention The invention relates to a heat polymerization process to produce a broad spectrum hydrocarbon resins, and more particularly a process which is intended to replace processes currently in use which rely upon the reaction of Friedel Crafts Catalysts.
Background Art In particular, the present invention relates to a novel continuous process for polymerization of aromatic monomers containing vinyl linkages, such as styrene, indene, vinyl toluen and higher and/or more complex aroraatics, as well as cyclic dien polymers, such as dicyclopentadiene and methyl cyclopentadiene, as well as other complex aliphatic monomers containing residual double bonds.
The process of the present invention yields broad spectrum, hydrocarbon resins having excellent color charac¬ teristics which provide formulating advantages in adhesives, paints, coatings and construction chemicals.
A particular advantage of the product produced by the process of the present invention resides in the production of a more reproducable polymer, having a regular repeating pattern as compared with a more random type of polymer that is produced with process utilizing Friedel Crafts Catalysts. Also, the present process achieves superior yields, as well as providing the capability of holding viscosity and melt point of the resulting polymer within narrower ranges as compared with the Friedel Crafts processes.
By "Friedel Crafts" processes is intended to mean the various polymerization processes involving the use of inorganic halides as catalysts. Such processes are markedly exothermic, and therefore present special problems in heat removal which further increases operational costs.
From the foregoing, it can be seen that the process of the present invention employs heat to generate free radicals, rather than relying upon Friedel Crafts Catalysts. While the present processes has operating temperatures in the range of 450°F to 600°F as compared with the lower Friedel Crafts processses temperatures, the higher operational temperatures for the present invention utilize the heat of polymerization to maintain the reaction temperatures.
With the operation of the present process in the 450° to 600°F range, there are accompanying pressures of 150 to 175 p.s.i. which maintain all reactants in the liquid state as compared with the low pressures of the Friedel Crafts reactions.
In the preferred form of the invention, the stream of reactants is pumped in the desired pressure range of 150 to 275 p.s.i. and lead through several passes of reaction section of piping in a continuous plug flow reactor in order that the reaction will proceed on a continuous basis. Also, static mixers are positioned in each length of piping to create or enhance turbulent flow to provide for faster reaction rates. Further¬ more, turbulence is promoted by the periodic use of reduced diameter piping in the continuous plug flow reactor sections to further increase velocity of fluid flow, thereby increasing mixing efficiency and reaction rates.
Yet another advantage of the present invention is that the present process does not require the expensive step of neutralization of catalysts as is the case in the Friedel Crafts processes.
Moreover, it has been found that the present processes gives higher resin yields. Also, the present process allows for the use of peroxide catalysts if desired.
Another feature of the present process is that it can be regarded as a continuous plug flow reactor system, and therefore yields the advantages of such a system. It will be clear that the present process can be used to produce other types of polymers that are polymerized by addition reactions.
As to products that can be polymerized, there is included those streams that are normally polymerized using Friedel Crafts Catalysts. This includes aromatic streams, such as aromatic, olefinic monomers, vinyl toluene, styrene. alphamethyl styrene, indene, coumarone, methyl coumarone, methyl indene and Cg-τ.2 alkyl aromatics.
The foregoing can be polymerized alone or in combinatio with any one or more of dicyclopentadiene, methydicyclopentadien and other complex alphatic hydrocarbons of the C5 to C20 fcYPe with residual active double bonds and other typical monomers which polymerize by addition reactions, such as acrylic and methacrylic mononers.
The continuous plug flow reactor of the present invention yields polymer with high conversion rates and free of residual impurities which are typical of acid polymerized polymers. The foregoing together with the use of stainless steel equipment and small amounts of antioxidant yields a product of excellent color, generally in the superior range of 6 to 8 on the Gardner Scale.
Referring now to the various figures of the drawing wherein like reference characters refer to like parts, specific attention is called to Figures 1 and 2 of the drawing. Figure 1 is a block diagram showing the basic process of the present invention, and Figure 2 is a view showing the various piping lengths comprising the reaction zone in a continuous plug flow reactor.
A specific example of feed stream involved with the process of the present invention involves the bringing together of 9315 pounds of styrene, 10,586 pounds of dicyclopentadiene, 6714 pounds of mineral spirits (a diluent), 42 pounds of an antioxidant and 2 pounds of cumene hydroperoxide.
After appropriate mixing, the aforesaid monomer blend is fed into a continuous plug flow reactor, such as shown in Figure 2. The reaction proceeds at approximately 500°F and a pressure of about 200 p.s.i.
In line mixers are provided along each leg of the continuous plug reactor shown in Figure 2. Short lengths of smaller diameter piping are also provided to connect each of the length of piping together, thereby further increasing the velocity and turbulence to promote a more uniform and faster reaction. The foregoing mixture of styrene, dicylopentadiene, mineral spirits, etc. is designated as reaction mixture which yields Product 1 as shown in the tables to follow. Product 2 is similar to Product 1, but its feed stream will be comprised of 20 to 25% by weight styrene, 20% by weight of a high aliphatic residual double bond material and the balance dicyclopentadiene, the same small amount of antioxidant and the same optional small amount of a peroxide catalyst.
The peroxide catalyst can be selected from various symmetrical and unsymmetrical peroxides as contained in British Patent No. 837,525, the disclosure of which is incorporated by reference. These included mono and di alkyl and aryl peroxides as exemplified by Bis (a,a-dimethylbenzyl) peroxide, as well as dicumyl peroxide and 2,5 dimethyl-2,5 di(t-butyl peroxy) hexane (sold under Trademarks Varox and Lupersol 101).
The Product 3 has a feed stream that is identical to Product 1 except Product 3 is 25% by weight styrene and 75% by weight cyclopentadiene.
The characteristics of the final polymerized products 1, 2 and 3 are shown in the accompanying table and data:
Sol ids : 70 % 70% 70 %
Type : Aroma t ic Aroma tic- Aliphatic Heat Reactive uαrull€
Color ( 50%) : 9-10 7-8 8 -9
Spec ial Features : Adhes ive Rule 66 Economical
Modifier Solubility
KEY BENEFITS:
Aliphatic Solubility
Low Color
Excellent Stability
Excellent Formulation Versatility
Excellent Heat Aging Characteristics
Economical
Chemical and Water Resistant
Chemically Neutral
Compatibility with Many Film Formers These hydrocarbon polymers will all add water and chemical resistance and increase tack in adhesive formulations, with Products I and II providing optimum results in adhesives.
Curing compounds will benefit from Product l's moisture resistance and Product Ill's quick flake off properties. All alkyd paints, will benefit from Product 2's aliphatic tolerance and quick dry. These three broad spectrum hydrocarbon resins excel in many applications. The following lists some of the mor traditional uses for these three products.
APPLICATIONS
I_ II III
ADHESIVES
Mastic X X X
Pressure Sensitive X X X
Rubber Cements X X X
COATINGS
Aluminum X X X
Can Coatings X X
Drum Enamels X X X
Emulsion X X X
Floor X X X
Industrial X X X
Marine X X X
Paper X
Traffic X X
CONSTRUCTION
Caulking Compounds X X X
Concrete Curing Compounds X X X
Cove Base and Panel
Adhesives X
Tile and Carpet Adhesives X
PHYSICAL PROPERTIES
_1 2_ _3
Solids 70±1% 70±1% 70±1%
Softening Point Ring and Ball Degree C 90-110 90-110 90-110
Color Gardner
As Supplied (70%) 9-13 8-12 9-12 at 50% in Toluene 8-12 7-11 7-9
Iodine Number 85-115 120-150 140-180
Viscosity
Brookfield #5 at lOrpm 11,600:1.2,000 6860±2,000 27,300_t5,000 at 77 degree F
Weight/Gallon (in pounds) 8.2-8.4 8.3-8.4 8.3-8.4
Resin Type Aromatic Aromatic Heat Aliphatic Reactive
MINERAL SPIRITS SOLUBILITY:
Product 1 is reducible in regular mineral spirits to 15-35% with a slight haze at room temperature. It may form a slight precipitate at cold temperatures which will dissolve on warming.
Product 2 has excellent solubility being soluble in Rule 66 Mineral Spirits to 12%.
Product 3 is reducible in regular mineral spirits to 14% and is clear at room temperature although there is some possibility of forming a haze and slight precipitation at cool temperatures.
OXIDATION AND HEAT STABILITY
Product: Initial Gardner Aged in Air Increase Color at 50% in 16 Hours at In Color Toluene 150 Degrees Units C
1 9-10 18 8 2 7-8 11-12 5 3 8-9 12-13 4 COMPATIBILITY
RESINS:
Styrene Butadiene Rosin Esters Vinyl-Toluene-Butadiene SBR Latex Phenolics Rosins Chlorinated Rubber Alkyds - Various
Long and Medium
PVA Emulsions
Styrene Acrylics Chlorinated Pariffin
OILS PLASTICIZERS
Linseed Refined and Bodied Phosphate Soya Bean Oil Phthalate Fish Oil Naphtenics Tung Oil
SOLVENT SPECIFICATION
Type: Proprietary Aliphatic Blend Flash Point: 120 degree F Closed Cup
I.B.P. : 320 degree F
50% 349 degree F
40% 478 degree F
EP: 672 degree F
API Gravi ■ty 25.5
Weight/Gaillon 7.4-7.6 lbs,
FDA STATUS
Products 1, 2 and 3 comply with FDA regulations:
175.105 Adhesives 176.170 Components of paper and paperboard in contact with Aqueous and fatty foods.
176.180 Components of paper and paperboard in contact with dry food. 177.1210 Closures with sealing gaskets for food containers. 177.2600 Rubber articles for intended repeated use. 178.3800 Preservatives for wood. In addition. Products II and III comply with FDA Regulation:
175.300 Resinous and Polymeric coatings.
From the foregoing, it can be seen that the process of the present invention involves bringing together in a feed stream, a styrene monomer, dicylopentadiene, mineral spirits, an antioxidant and optionally a peroxide, followed by heating the feed stream in a reaction zone at a temperature range of from 450°F to β00°F and at a pressure of 150 p.s.i. to 175 p.s.i., while moving the feed stream at a rate of from 2,400 to 5,000 pounds per hour through the reaction zone constituting a continuous plug flow reactor, and removing the resultant polymer from the reaction zone.
Without further elaboration, the foregoing will so fully illustrate my invention that others may, by applying current or future knowledge, readily adopt the same for use under various conditions of service.

Claims

What is claimed as the invention is:
1. A heat polymerization process to produce broad spectrum hydrocarbon resins, said process involving bringing together in a feed stream, a double bond containing material, mineral spirits, and an antioxidant, heating said feed stream in a reaction zone at a temperature range of from 450°F to 600°F an at a pressure range of 150 to 275 p.s.i. while moving the feed stream at a rate of from 2400-5000 pounds per hour through the reaction zone, and removing the resultant polymer from the reaction zone.
2. The process of Claim 1 wherein said double bond containing material is styrene.
3. The process of Claim 1 wherein a peroxide catalyst is also used.
4. The process of Claim 1 carried out in a continuous plug flow reactor.
5. The process of Claim 1 which involves also bringing together dicyclopentadiene is said feed stream.
PCT/US1987/002949 1986-11-07 1987-11-05 Heat polymerization process to produce broad spectrum hydrocarbon resins WO1988003538A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US92844486A 1986-11-07 1986-11-07
US928,444 1986-11-07

Publications (1)

Publication Number Publication Date
WO1988003538A1 true WO1988003538A1 (en) 1988-05-19

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WO (1) WO1988003538A1 (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5166260A (en) * 1989-05-24 1992-11-24 Montedipe S.R.L. Process for the continuous bulk production of high impact vinylaromatic (co)polymers
US5171793A (en) * 1990-02-22 1992-12-15 Exxon Chemical Patents Inc. Hydrogenated resins, adhesive formulations and process for production of resins
NL1009903C2 (en) * 1998-08-20 2000-02-22 Dsm Nv Tubular reactor, method and apparatus for high pressure polymerization.
US10961337B2 (en) 2016-12-12 2021-03-30 Hanwha Chemical Corporation Method of preparing dicyclopentadiene-based resin and dicyclopentadiene-based resin

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2371499A (en) * 1942-04-18 1945-03-13 Dow Chemical Co Modified polymerization of vinyl aromatic compounds
CA513391A (en) * 1955-05-31 The Distillers Company Limited Thermal polymerisation of alpha methyl styrenes
US2921932A (en) * 1954-01-28 1960-01-19 Monsanto Chemicals High pressure polymerization of styrene
US2951061A (en) * 1956-02-16 1960-08-30 Phillips Petroleum Co Process and apparatus for contacting materials
GB859517A (en) * 1957-12-17 1961-01-25 Koppers Co Inc Improvements in or relating to the polymerisation of vinyl aromatic compounds
US3679651A (en) * 1968-08-29 1972-07-25 Mitsui Toatsu Chemicals Method of polymerizing styrene
CA1068047A (en) * 1976-11-23 1979-12-11 George F. Adams Reaction process and apparatus for continuous polymerization
US4209599A (en) * 1977-01-15 1980-06-24 Synres International B.V. Continuous mass preparation of polymers

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA513391A (en) * 1955-05-31 The Distillers Company Limited Thermal polymerisation of alpha methyl styrenes
US2371499A (en) * 1942-04-18 1945-03-13 Dow Chemical Co Modified polymerization of vinyl aromatic compounds
US2921932A (en) * 1954-01-28 1960-01-19 Monsanto Chemicals High pressure polymerization of styrene
US2951061A (en) * 1956-02-16 1960-08-30 Phillips Petroleum Co Process and apparatus for contacting materials
GB859517A (en) * 1957-12-17 1961-01-25 Koppers Co Inc Improvements in or relating to the polymerisation of vinyl aromatic compounds
US3679651A (en) * 1968-08-29 1972-07-25 Mitsui Toatsu Chemicals Method of polymerizing styrene
CA1068047A (en) * 1976-11-23 1979-12-11 George F. Adams Reaction process and apparatus for continuous polymerization
US4209599A (en) * 1977-01-15 1980-06-24 Synres International B.V. Continuous mass preparation of polymers

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5166260A (en) * 1989-05-24 1992-11-24 Montedipe S.R.L. Process for the continuous bulk production of high impact vinylaromatic (co)polymers
US5171793A (en) * 1990-02-22 1992-12-15 Exxon Chemical Patents Inc. Hydrogenated resins, adhesive formulations and process for production of resins
NL1009903C2 (en) * 1998-08-20 2000-02-22 Dsm Nv Tubular reactor, method and apparatus for high pressure polymerization.
WO2000010701A1 (en) * 1998-08-20 2000-03-02 Dsm N.V. Tubular reactor, process and installation for high-pressure polymerization
US10961337B2 (en) 2016-12-12 2021-03-30 Hanwha Chemical Corporation Method of preparing dicyclopentadiene-based resin and dicyclopentadiene-based resin

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AU8321987A (en) 1988-06-01

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