Classifications

• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
  • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
  • D21H17/20—Macromolecular organic compounds
  • D21H17/33—Synthetic macromolecular compounds
  • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
• • 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
  • C08F289/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds not provided for in groups C08F251/00 - C08F287/00
• • 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
  • C08F8/00—Chemical modification by after-treatment
  • C08F8/46—Reaction with unsaturated dicarboxylic acids or anhydrides thereof, e.g. maleinisation
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
  • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
• • 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
  • C09J157/00—Adhesives based on unspecified polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
• • 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
  • C08F212/00—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
  • C08F212/02—Monomers containing only one unsaturated aliphatic radical
  • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
  • C08F212/06—Hydrocarbons
  • C08F212/08—Styrene
• • 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
  • C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
  • C08F2800/20—Copolymer characterised by the proportions of the comonomers expressed as weight or mass percentages
• • 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
  • C08F2810/00—Chemical modification of a polymer
  • C08F2810/30—Chemical modification of a polymer leading to the formation or introduction of aliphatic or alicyclic unsaturated groups

Definitions

• the present invention relates to a process for the manufacture of hydrocarbon resins using hydrocarbon as a raw material and sizing agents for paper in which the obtained hydrocarbon resins are used.
• hydrocarbon resins have been generally used as a raw material for floor material, road pavement, paint, rubber compounding agent, adhesive, molded laminate, etc.
• rosins have been normally used as a main ingredient for the sizing agent for paper making, but recently it has been proposed that a hydrocarbon resin be used as the sizing agent for paper making in place of rosin.
• Various investigations for using hydrocarbon resin for sizing agent have been made. For example, it has been known to manufacture a paper sizing agent using the hydrocarbon resin by adding and treating hydrocarbon resin with unsaturated acid and/or rosin.
• unsaturated hydrocarbon in a fraction which is obtained in a cracking and reforming of petroleum has a boiling point of more than 130 C. and is aromatics-rich is used.
• the sizing efliciency of the hydrocarbon resin which is used with such aromatics-rich fraction as the raw material is not often reached to the sizing efiiciency simi- I lar to that of fortified rosin sizing agent depending upon paper making conditions, even if the hydrocarbon resin is modified by adding rosin, unsaturated acid, etc. thereto.
• the sizing efficiency is bad when the temperature of paper making is low.
• hydrocarbon resin as a paper sizing agent is still unsatisfactory.
• the first object of the present invention is to provide a process for the manufacture of hydrocarbon resins capable of being used as a sizing agent for paper and paper board having an excellent efiiciency.
• the second object of the present invention is to provide the said hydrocarbon resins with a sizing efficiency of which is not decreased even if a lower surface temperature of the paper in a paper making machine, such as 80 C., is used for the drying and which can provide a excellent sizing agent having no objection even when a larger amount of it is added to make a hard sized paper.
• a further object of the present invention is to provide a process for the manufacture of the sizing agent.
• heavy petroleum fraction such as light naphtha, heavy naphtha, gas oil, etc. may be cracked in a short time and under a comparatively low pressure in presence of steam at a temperature of 500 to 900 C.
• Hydrocarbons derived from such a steam cracking process usually consist of a considerably large amount of diolefin, olefin, aromatic hydrocarbon and some paraffin.
• a fraction containing hydrocarbons having carbon atoms of more than 8 from which a fraction containing hydrocarbons having atoms of 1 to 7 is removed by a continuous fractional distillation containing a large amount of unsaturated hydrocarbon, for example a fraction having a boiling point of 130 to 300 C. has nearly the following composition:
• the low boiling hydrocarbons to be used as the added component in the process of the present invention it is possible to use unsaturated hydrocarbons having carbon atoms of 4 to 5 such as butene, butadiene, pentene and pentadiene which are obtained as by-product from the cracking or the reforming of petroleum and have a boiling point in range of -15 to 45 C., but the preferable one is hydrocarbon containing mainly 4 carbon atoms which has a boiling point in range of l5 to 15C. and contains olefins and diolefins such as butene and butadiene.
• unsaturated hydrocarbons having carbon atoms of 4 to 5 such as butene, butadiene, pentene and pentadiene which are obtained as by-product from the cracking or the reforming of petroleum and have a boiling point in range of -15 to 45 C.
• the preferable one is hydrocarbon containing mainly 4 carbon atoms which has a boiling point in range of l5 to 15C
• composition of the preferable one is for example unsaturated hydrocarbon-rich fraction having the following composition:
• This low boiling fraction may vary depending upon various properties of the hydrocarbons boiling above 130 C. such as boiling range, the degree of unsaturation and content of aromatic hydrocarbon as well as various properties such as boiling range and contents of olefin and diolefin of low boiling fraction to be added, but when each fraction which is shown in the after-mentioned examples is used it is normal to use less than 200 parts by weight of the low boiling fraction per 100 parts by weight of high boiling fraction.
• the polymerization in the process of the present invention can be carried out by various methods such as radical and ionic polymerization, but most normal method is one in which cationic type polymerization catalyst such as aluminium trichlo-ride, aluminium tribromide, boron trifluoride, titanium tetrachloride, ferric chloride is used. These catalysts can be used in solid, liquid or gaseous states, but it is convenient to use them in form of liquid. Although the amount of these catalyst may be varied, it is practical to use these catalyst in an amount of 0.5 to 3.0% by weight of the raw material unsaturated hydrocarbon.
• cationic type polymerization catalyst such as aluminium trichlo-ride, aluminium tribromide, boron trifluoride, titanium tetrachloride, ferric chloride.
• the polymerization temperature may be varied in a wide range, but the preferable temperature is -80 to 80 C. In order to carry out the polymerization at a high emperature, it is necessary to use a polymerization vessel which is pressure resist-ant.
• the polymerization time in case of a batch type, is preferable 0.5 to 10 hours, but a suitable time is normally l to 5 hours.
• the addition of the low boiling fraction to the high boiling fraction may be carried out before, after or when the catalyst is added to the high boiling fraction, or the low boiling fraction to which a part of the catalyst was already added may be added to the high boiling fraction, but in any case a hydrocarbon resin which has a superior sizing property can be obtained by suitable regulating the polymerization time and the amount of catalyst.
• the reaction liquid in which the polymerization was completed is generally added with an aqueous alkali or an alcoholic alkali to decompose and deactivate the catalyst and then the reaction product treated with alkali is washed with water or water containing a little quantity of alcohol. At that time the reaction product liquid is heated to remove unreacted low boiling fraction in the form of gas from the former. The pale yellow transparent liquid is obtained. The reaction liquid which is obtained as a pale yellow transparent liquid is stripped under a reduced pressure to obtain the product hydrocarbon resin as a residue.
• the polymerization process according to the present invention can be carried out by a batch type and continuous type can also be used.
• the hydrocarbon resins which are obtained by these polymerization method is satisfactorily used for a sizing agent.
• the present invention is illustrated but not limited by the following examples and comparative examples in which the parts and percentages are by weight.
• Example 1 100 parts of a hydrocarbon fraction which were obtained in a steam cracking of petroleum, had a boiling point of 130 to 240 C. and contained 52% of styrene, indene and their derivatives, 39% of other aromatics, 3% of olefin, less than 1% of diolefin and 5% of parafiin and naphthene were added with 20 parts of a hydrocarbon fraction which had a boiling point of l to 15 C. and contained 34% of olefine; 42% of diolefin and 24% of paraffin. To the mixture was added 1% of boron trifluoride-phenol complex as catalyst and the mixture was then polymerized at the temperature of 30 C. for 3 hours.
• the reaction liquid was added with 10% of 10% aqueous sodium hydroxide solution and then was heated at the temperature of 80 C. and an atmospheric pressure. At that time, 6 parts of unreacted low boiling fraction were removed as a gas.
• the reaction product was washed with a hot water of 50 C. in 3 times and thereafter was heated to 180 C. under a reduced pressure of mm. mercury to remove a unreacted matter and low polymers. As a result, 54 parts of a pale yellow hydrocarbon resin were obtained.
• Example 2 The procedure described in Example 1 was repeated except that 10 parts of a hydrocarbon fraction which had a boiling point of l0 to 0 C. and contained 31% of olefin, 54% of diolefin and of parafiin were used, 52 parts of hydrocarbon resin were obtained. In this case, 2.5 parts of gas were removed.
• Example 3 The procedure described in Example 1 was repeated except that parts of a hydrocarbon fraction which had a boiling point of l5 to 10 C. and contained 28% of olefin, 42% of diolefin and 30% of paraffin were used. 59 parts of hydrocarbon resin were obtained. In this case, 14 parts of gas were removed.
• Example 4 100 parts of high boiling hydrocarbon described in Example 1 were added with 100 parts of low boiling hydrocarbon described in Example 3. The mixture was added with 1% of boron trifiuoride-ethylether complex as a catalyst, and were polymerized at the temperature of C. for 5 hours. The polymerization liquid was added with 10% sodium hydroxide methanolic solution in the amount of 10% based upon the raw hydrocarbon mixture.
• Example 1 The mixture was agitated was then raised to a room temperature was thereafter added with 10% of water and then was heated to the temperature of C. Further operation was carried out as described in Example 1. 81 parts of hydrocarbon resin was obtained. In this case, 35 parts of gas were removed.
• Example 5 parts of the high boiling hydrocarbon oil as described in Example 1 were added with 30 parts of hydrocarbon containing 58% of olefin and 42% of parafifin which was obtained by removing diolefin from a hydrocarbon fraction boiling in 10 to 15 C. as used in Example I.
• 48 parts of the high boiling hydrocarbon resin were obtained. In this case, 18 parts of gas were removed.
• Example 6 100 parts of hydrocarbon fraction oil as described in Example 1 were added with 30 parts of hydrocarbon fraction which had a boiling point of -l5 to 45 C. and contained 52% of olefin, 30% of diolefin and 18% of parafiin. By the same operation as described in Example 1, 52 parts of hydrocarbon resin were obtained. In this case, 6.5 parts of gas were removed.
• Example 7 100 parts of the high boiling hydrocarbon fraction oil as described in Example 1 were added with 20 parts of hydrocarbon fraction which had a boiling point of 0 to 45 C. and contained 48% of olefin, 32% of diolefin and 20% of parafiin. By the same operation as described in Example 1, 54 parts of hydrocarbon resin were obtained. In this case 7 parts of gas were removed.
• Comparative Example 2 100 parts of the high boiling hydrocarbon fraction oil as described in Example 1 were added with parts of hydrocarbon fraction which had a boiling point of 60 to 100 C. and contained 31% of olefin, 8% of diolefin, 18% of paraflin and 43% of aromatics. By the same operation as described in Example 1, parts of hydrocarbon resin were obtained.
• Comparative Example 3 resin of the present invention cannot be ascertained by a simple supposition, it can be completed only by repeating investigation of various hydrocarbon resins and vari ous dispersing or solubilizing processes with a consideration for the very delicate function of paper sizing.
• a hydrocarbon resin which have a higher reactivity for the above acid component can be obtained by using the raw materials other than the fraction used in the present invention.
• the reactivity for the acid component of the known resins is same as the novel TABLE L-FROPERTIES OF HYDROOARBON RESINS OBTAINED IN ABOVE EXAMPLES AND COMPARATIVE EXAMPLES Examples Comparative exampies Softening point C.) 70 75 67 69 72 81 73 olor 2 12 12 12 10 12 12 11 12 14 12 Bromine value" 51. 2 45. 0 58. 0 82. 8 37. 2 50. 5 59. 4 32. 0 44. 5 52. 2 Acid value O. 3 0. 2 0. 1 0. l 0. 1 0. 2 0. 2 0.
• hydrocarbon resins of the present invention are used by themselves as a sizing agent for paper and paper board by applying them a conventional emulsifying method, they give a superior efficiency to the emulsion of hydrocarbon resin which raw material is a fraction containing large amount of aromatichydrocarbons having a boiling point of more than 130 C.
• the characteristic of the present invention is considerable exhibited by incorporating the hydrocarbon resin which is obtained in the process of present invention with a,B-unsaturated aliphatic acids or acid anhydride, and then by adding and mixing with at least one compound (hereinafter refer to rosin and the like) selected from the group consisting of rosins, higher fatty acids and their a,,8-unsaturated aliphatic acids or acid anhydrides partially adducts and thereafter by dispersing or solubilizing into water while the mixture is saponified with alkali.
• rosin and the like selected from the group consisting of rosins, higher fatty acids and their a,,8-unsaturated aliphatic acids or acid anhydrides partially adducts
• this novel hydrocarbon resin is especially suitable for the application of the abovementioned dispersing or solubilizing, it gives very easily a stable dispersion or solution, and also the sizing efiiciency is very higher than that of paper sizing agents which are used with any prior hydrocarbon resins, and is not changed by the variation of paper making conditions.
• the hydrocarbon resin of the present invention gives a considerable sizing efiiciency by reacting it with nip-unsaturated aliphatic acids or acid anhydride to form a partically addition-reacted product, the sizing efiiciency is not influenced even if the amount of the acids is increased. On the contrary, the stability of dispersion and the transparency of the prior hydrocarbon resin are increased when the addition amount of acid to the resin is increased more than but the sizing eficiency is rather decreased.
• this novel hydrocarbon resins have a property which is suitable for applying water dispersing or solubilizing process wherein the novel resins are reacted with o h-unsaturated aliphatic acids or acid anhydride to form a partially addition-reacted resin and the resulting resin and then the mixture is mixed and heated with rosin and the like and thereafter is saponified with alkali.
• a very useful sizing agent by the combination of these two arts, i.e. the manufacturing arts of the hydrocarbon resin and the sizing agent using the resin according to the present invention.
• Suitable acidic compounds containing the group include a d-unsaturated aliphatic acids or acid anhydrides, such as acrylic, methacrylic, crotonic, maleic, fumaric, itaconic and citraconic acids and their acid anhydrides. Further citric acid and the like may be mentioned as a compound producing ,fi-Ui'lSfitlll'EltCd polybasic acid by heating. Among them, as monobasic acid has the property which can be polymerized itself by a heating, it is convenient to use dibasic acid.
• the rosin and the like which are used in the present invention can give an effect for the dispersing into water of hydrocarbon resin which is added and reacted with n p-unsaturated aliphatic acids.
• the employing amount of it is sufiicient to use in a small amount because the dispersing into water of the resin is very easy. Namely, it is sufiicient to use it in an amount necessary for a dispersing agent and therefore the necessary amount of it is smaller than in the case that sizing agent is manufactured from the prior hydrocarbon resin.
• rosins and higher fatty acids there are mentioned gum rosin, wood rosin, tall oil rosin, FF rosin, tall oil, soybean oil fatty acid, linseed oil fatty acid, coconut oil fatty acid, stearic acid, oleic acid, linoleic acid, etc.
• suitable employing amount is as shown in the hereinafter mentioned examples, the suitable amount should be selected according to the addition-reaction amount of a,[3-unsaturated aliphatic acids or acid anhydrides for hydrocarbon resins or above rosins or higher fatty acids.
• alkali salt of the present hydrocarbon resin containing carboxylic group, rosin and the like is very good dispersibility into water. It is sufficient to treat the above resin mixture together with suitable aqueous alkali solution in a saponifying vessel or emusifying equipment having a conventional agitator and then to dilute the treated matter with water to a desired concentration.
• alkali it is possible to use hydroxide and/or carbonate of alkali metal, ammonium hydroxide, organic amines, etc.
• a process for sizing various paper and paper boards with the sizing agent of the present invention is not different from the prior rosin sizing process and therefore the process can be carried out in any paper machine without a trouble. As carried out generally, namely, the
• the pulp suspension is made acidic and is sheeted on a wire and thereafter the sheet is dried.
• the hydrocarbon resin of the present invention when used as a sizing agent for paper making, an influence for sizing efiiciency of drying temperature at the paper making is almost negligible and the excellent sizing efiiciency can be obtained by the use of small amount of u,B-unsaturated acid and rosin. Therefore, the present sizing agent is technically and economically superior than the prior sizing agent.
• the hydrocarbon resins obtained by the process of the present invention is of use not only as a sizing agent but also a raw material for floor material, road pavement, paint, rubber compounding material, adhesive, molded laminate, etc.
• Example 8 Ten kinds of hydrocarbon resins which were obtained in Examples 1 to 7 and Comparative Examples 1 to 3 were treated as follows, respectively:
• Amount of sizing agent added 0.5% by weight 1.0% by weight 0.5% by weight 1.0% by weight Sizing degree (sea):
• Example 9 The composition of tall oil used were as follows:
• Example 1 100 kg. of each hydrocarbon resin in Example 1 and Percent Comparative Example 1 were incorporated with 10 kg. 45 of maleic anhydride, respectively.
• the mixture was addi- 2O QIeICaCId 23 tion reacted in the reactor and under the same reaction Llnohc acld 18 conditions as described in Example 8 and then was other fafty aclds 7 added with 50 kg. of gum rosin by a similar operation. Unsaponlfied matters 7 Thus, a transparent brown solid resin was obtained.
• the s'aponification value and softening point of the obtained resins were 113 and 79 C. in the resin of Example 1 and 113.5 and 81 C. in the resin of comparative TABLE 5.COMPARISON BETWEEN SIZING DEGREE Drying Conditions of Sheet 80 C., 5 mins. 110 0., 5 mins.
• the sizing agents which were obtained by applying the which is aliphatic unsaturated hydrocarbon-rich in an process of Examples 8 and 9 to the hydrocarbon resins aromatic-rich hydrocarbon fraction boiling in a range of of Example 1 and Comparative Example 1 refer to 130 C. to 300 C. which was obtained as lay-product 1-8, Cl- 8, 1-9 and Cl-9, respectively.
• the from the cracking or reforming of petroleum in an sizing efficiency of l-8, CL-8, 1-9 and Cl-9 amount of 0.1 to 1 part by Weight of the low-boiling are shown in Table 4.
• the measuring conditions are the fraction per part by weight of the high-boiling fraction same as described in Example 8. and polymerizing the mixture thus obtained at a tem- TABLE 4.OOMPARISON BETWEEN SIZING DEGREE Drying Conditions of Sheet 80 C., 5 mins. 110 0., 5 mins.
• Amount of sizing agent added (resin amount/dry pulp by weight)- 0.5% by weight 1.0% by Weight 0.5% by weight 1.0% by weight Sizirlig degree (see):
• Example 10 perature of 80 C. to 80 C. in the presence of a cationic type polymerization catalyst.
• a sizing agent for making paper and paper board consisting essentially of an aqueous dispersed or solu- 5 bilized product which was obtained by reacting 100' parts by weight of a hydrocarbon resin with 5 to 10 parts by weight of a compound selected from the group consisting of an alpha,beta-unsaturated aliphatic dicarboxylic acid
• hydrocarbon resins which were obtained in Examples 1 and 4 as well as Comparative Examples 1 and 2 were treated by applying the operation and condition as described in Example 8, using itaconic acid, tall oil and triethanol amine.
• the incorporating ratios of materials and properties of treated resins were as follows and acid 'anhydride thereof to form a partial addition Hydrocarbon resin kg 100 reaction product thereof, mixing (1) the product thus Itaconic acid kg 5 obtainedd With (2) 10 to 50 parts by weight, based on 100 Tall oil kg- 25 parts by weight of the hydrocarbon resin used, of at Saponi-fication value of treated resin 66.2 least a member selected from the group consisting of Softening point of treated resin C 67 rosins, higher fatty acids, -alpha,beta-unsaturated aliphatic Triethanol amine kg 11.2 dicarboxylic acid partial adducts of rosins, alpha,beta- 1 1 unsaturated aliphatic dicarboxylic acid anhydride partial adducts of rosins, alpha,beta-unsaturated aliphatic dicarboxylic acid partial adducts of fatty acids and alpha,betaunsaturated aliphatic dicarbox

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• General Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Paper (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

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Cited By (7)

Citations (9)

• 0
  • GB GB1054759D patent/GB1054759A/en active Active
• 1964
  • 1964-03-31 US US356046A patent/US3379663A/en not_active Expired - Lifetime
  • 1964-04-02 DE DE1520376A patent/DE1520376C3/de not_active Expired
• 1965
  • 1965-04-30 AU AU58229/65A patent/AU415903B2/en not_active Expired

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