• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    . A method for producing mixed cellulose simple ethers by treating mercerized cellulose with esterifying agents followed by washing and drying the target product, characterized in that, to obtain esters with a lower flocculation temperature during hydrophilicity, the treatment was conducted with 0.2. including alkyl chloride, 0.025-0.82 May. including ethylene oxide, 0.4-1.4 May. including propylene oxide and / or 0.089-0.9 May. including butylene oxide. 1 May. including cellulose to the degree of substitution by alkyl 0.1-0.8, exciethyl 0.5-1.5, hydroxypropyl 0.5-2.0 and / or hydroxybutyl 0.1-1.0.
    公开号:SU1105118A3
    申请号:SU742005714
    申请日:1974-03-13
    公开日:1984-07-23
    发明作者:Георг Линденфорс Свен；Йохан Вестберг Свен-Олоф
    申请人:Мо До Кеми Аб (Фирма)；
    IPC主号:
    专利说明:

    ate
    This invention relates to chemical technology, specifically to the production of mixed ethers, which have specific properties that can be used as binding agents, thickeners and film-forming agents. A known method of producing a mixed cellulose ether, β-alkyl oxyalkyl cellulose, by treatment of alkali cellulose with an alkyl halide and alkylene oxide. However, in this method, cellulose ethers are obtained, which, depending on the substituents, have hydrophilicity and flocculation temperature of 100 ° C, or hydrophobicity and flocculation temperature below 55 ° C, which equally limits the possibility of using these products in aqueous solutions. The closest to and inventive is a method of obtaining a simple mixed cellulose ether, which consists in the fact that the mercerized cellulose is treated with esterifying agents, ethylene oxide and propylene oxide in an organic solvent at 20-140 ° C to the necessary degrees of substitution, followed by washing and drying the target product 2. However, the known method also does not allow the preparation of mixed cellulose ethers having a reduced flocculation temperature with increased hydrophilicity. The aim of the invention is to obtain cellulose ethers with a reduced flocculation temperature with increased hydrophilicity. This goal is achieved by the fact that according to the method of preparing mixed cellulose ethers by treating mercerized cellulose with esterifying agents, followed by washing and drying the target product, the treatment is carried out between 0.2 and 10 May. including alkyl chloride CJ-GV, 0.025-0.82 wt.h. ethylene oxide, 0.4-1.4 May. including propylene oxide and / or 0.089-0.9 May. including butylene oxide on 1 May. including cellulose to the degree of substitution by alkyl 0.1-0.8, hydroxy ethyl 0.5-1.5, hydroxypropyl 0.5-2.0 and / or hydroxybutyl 0.1-1.0. The rio non-ionic cellulose ethers of the invention are obtained by the reaction between cellulose 8a, mercerized alkali metal hydroxide and ethylene oxide and / or butylene, and at least one alkyl halide having 2-4 carbon atoms in the presence of an organic reaction medium, and the resultant The cellulose ether can be washed and the remaining part of the alkali metal hydroxide can be neutralized, after which the cellulose ether is dried to a solids content of approximately 90% by weight. An inert organic solvent, such as xylene, acetone, pentane, hexanol or dichloromethane, JIO is preferably used as the reaction medium, halo, alkyl alkyl - ethyl chloride, butyl chloride, propyl chloride, ethyl bromide, etc., since such compounds can be used as reagents for introducing a suitable alkyl group into the cellulose ether. The method includes the suspension of cellulose, mercerized alkali metal hydroxide in the reaction medium, including at least one alkyl chloride having: 2-4 carbon atoms, alkoxylation | with ethylene oxide and propylene oxide and / or butylene oxide at 50-75 0 and its alkylation with alkyl chloride having 2-4 carbon atoms at 70120 ° C, preferably at 90-115 ° C and preferably at 100-110 ° C. Moreover, the reaction medium, which also serves as an alkylating agent, is present in an amount of 0.2-5 May 0 hours, preferably 0.4-3.0 May. hours on May 1. including pulp. Cellulose is a soluble form of wood pulp or cotton fluff and can be used in the form of sheets, flakes or powder. The mercerization step is usually carried out using sodium hydroxide with a concentration of 10-50%, especially 1530%, preferably 18-24%, at 10-30 ° C for 15-180 minutes. The mercerized cellulose is then squeezed to a spin degree of 2-3.5. The proposed method is sufficient 1.2 miles of alkali per 1 mole of anhydroglucose unit. The mercerized squeezed pulp mass is crushed or milled, after which it is introduced into the autoclave. The main part of the oxides of the blefins are added at 50-75 ° C, while the alkyl halide reacts at 70-120 ° C. Olefin oxides are introduced in one or several portions, and ethylene oxide is introduced at the beginning of the process. Ethylene oxide is more reactive than other olefin oxides and forms primary hydroxyl groups, which more easily react with propylene oxide and butylene mow than secondary hydroxyl groups. Ethylene oxide, propylene oxide and butylene oxide are loaded in more than double the amounts expected in the reaction.
    In the preparation of cellulose ethers, some ingredients, such as low molecular weight alcohols and ethers, are added to the reaction medium, which improves the properties of the product when alkyl hydroxyalkyl cellulose ethers are prepared. Moreover, the addition of ethylene oxide to cellulose is promoted with additives, while the alkylation is inhibited and the amount of, for example, ethyl groups that is supplied to the analysis, is introduced only at 80 ° C.
    In the case where substantially pure alkyl halide having 2-4 carbon atoms is used as the reaction medium, cellulose ethers containing hydroxyethyl and higher molecular weight hydroxyalkyl groups can be alkylated at normally low temperatures. Therefore, you can enter alkyl groups at temperatures below 70 ° C.
    Cellulose ethers are widely used, for example, cellulose ethers can be admixed with acrylate-base dyes to form latex films having a high transmission (bandwidth). For this purpose, cellulose ethers having a molecular substitution which corresponds to a flocculation temperature in the range of 60-70 ° C are particularly suitable. In this case, a relatively high flocculation temperature is desirable since it must be close to the temperature at which the latex is treated. at the factory and during storage. Cellulose ethers are also used as thickeners, for example, in food products, as binding agents in adhesives, as well as consistency improving agents and stabilizers. Moreover, cellulose ethers can be used in final compositions for textile industry and as coating compositions for paper and paper products. If the molecular substitution with hydroxypropyl or oxybutyl groups is large, the cellulose ethers acquire excellent thermoplastic properties. By controlling the amount of ethylene oxide added to the cellulose, it is possible to change the solubility of ether in water from the state of complete insolubility to high solubility without loss of thermoplastic properties. In addition, cellulose ethers with different water solubility and different flocculation temperatures can be obtained by the simultaneous introduction of propylene oxide and butylene oxide into cellulose and a change in their mutual ratio. Thermoplastic cellulose ethers can be used alone or with other plastics to produce plastic sheets (coatings), for example for use in the packaging or textile industry or as binding agents for varnishes and other dyes.
    Example 1. Sheet pulp with a degree of polymerization (SP)
    - 1000, suitable for the production of cellulose acetate in an amount of 1 May. hours mercerized with a 20% aqueous solution of sodium hydroxide for 30 minutes at room temperature. After graduation
    mercerization the cellulose was pressed to a degree of spin 2.5. The alkaline pulp is crushed and sent to an autoclave. Air is pumped out of the autoclave and the mixture is fed for 1.5 May. h. chlorine of that ethyl, 1.4 May. including propylene oxide and 0.3 May. including ethylene oxide. Then the temperature in 30 minutes is raised to 70 C at 70 ° C for 3 hours. After this reaction
    the remaining ethyl chloride is discontinued and withdrawn. The reaction product is settled in hot water at 95 ° C, and the remaining alkali is neutralized with acetic acid. After dewatering, drying and grinding, the product is analyzed and a part of it is dissolved to determine the transparency, viscosity, content of fibrous materials and flocculation temperature. Transparency is determined by the usual method of bandwidth at 550, and the viscosity is determined with a Brookfield LVT viscometer at 20 ° C. The analysis revealed that the product is cellulose ether having a molecular substitution M3r, (.j, , y, 0.7, M3gi | roxypropyl 2.0, degree of substitution of NW, 0.25, viscosity 3650 cP; transparency 96.9%, content of fibrous material O, flocculation temperature 63.5 ° C. Found very high degree of molecular substitution with hydroxyalkyl, taking into account the loaded amounts of alkyl oxides.
    Examples 2-5. Cellulose ethers are prepared as in Example 1, except that cellulose with SP 500 is used and the amount of propylene oxide is varied from 0.7 to 1.4 May. hours on May 1, including dry weight. The data obtained are given in table.1.
    Table 1
    Propylene oxide, May. h. / May. h. dry maeey
    MH,
    njxpOK
    SIETPA
    MOH
    gmaro sipropi
    3
    . ethyl
    Viscosity, fc Transparency,% Fiber content,
    Flocculation temperature, ° С From table. 1 shows that the above. the addition of fine propylene results in products with more transparent and lower flocculation temperatures. Addition 1.4 May. h. oxide kerf on May 1. including cellulose, corresponding to approximately 4.0 propylene oxide molecules per anhydroglucose cellulose unit, results in a cellulose derivative
    1.4
    0.7
    2.0
    0.25
    2450
    95,8
    ABOUT
    69
    64
    77 very high strength and very low fiber content. However, cellulose ether has a high viscosity of 2450 cP, that is, it has a very high quality. Examples 6-15. The examples are carried out analogously to example 1, except that the amount of ethyl chloride is changed, as shown in the table below. 2. The results are summarized in Table 2. The reaction medium, in hours (May 1, one eell cellulose about 0.2 0.4 0.4 0.6 0.7 GI {(, roxisgia 0.4 1.8 1.8 YMAipokcvinponn 0.1 0.2 640 1720 3370 Viscosity, eP Ease,% 95.7 97.1 96.7 Fiber content,% 0.200 flocculation temperature, ° С 98.0 71.0 68.5
    Thus, the use of ethyl chloride in quantities of 0.4 to 2, 5 May. hours on May 1. Part of the pulping results in the production of cellulose ethers that meet the important requirements for viscosity, transparency and fiber content. The relatively low temperature of flocculation of cellulose ethers suggests a high conversion of ethylene oxide. From the data obtained in example 15, it follows that with a high content of ethyl chloride and a major part of the cellulose in the reaction in the reaction, the final product does not have such good properties as in the case when the amount of the reaction medium is 0.4-2.5 May h
    Examples 16-19. The viscose mass (SP pulp 850) measures the Table 2
    Routing with 20% aqueous solution of sodium hydroxide for 30 minutes, then squeezing to a degree of extraction of 2.5. Mercerized cellulose is crushed and placed in an autoclave, which is loaded 1.5 May. -h chlorinated ethyl, as well as ethylene and butylene butyl in the amounts indicated in the table. 3. After heating from 30 to 70-75 ° C for 30 minutes, the reaction mixture is kept at this temperature for 3 hours. The resulting reaction product is settled at 95 ° C in water and simultaneously neutralized with acetic acid. The product is dehydrated, dried, and ground, and then dissolved to determine the transparency, fiber content, viscosity, and flocculation temperature. The results are presented in table. 3. 0,6 0,751,01,5. 2,53,510,0 0,7 0,70,70,70,70,70,5 1,9 2,02,02,02,01,91,3 0, 2 0.20,250,2500,2502,00,1 4520 43704560356036701600980 96.0 95,597,396,997,195,087.0 0000000 66.5 64.0 64.5 63.5 63.0 67.0 82.0
    Ethylene oxide, wt. H (1 m.h., dry weight)
    Butylene oxide, ma.ch. (1 lb. weight of mass)
    The resulting cellulose ethers are of high quality and form solutions of high transparency and low fiber content. From the above examples, it can be seen that the flocculation temperature can be controlled by simply controlling the reaction temperature and the amount of ethylene oxide and butylene oxide.
    Examples 20-23. Mercerized clean paper
    1105118
    ten
    Table 3
    0.82
    0.55
    0.82
    0.90
    0.68
    0.90
    the mass (SP of cellulose 1300) is subjected to apcoxyly & nium by ethylene quills, by butyl queniline, and propylene oxide, in amounts of 0.27, 0.72 and 0.089, respectively, 0.27 May. hours on May 1. including dry pulp. The reaction is carried out at 1.5 May. including ethylene chloride on 1 May. including cellulose for 150 minutes at 75 ° C. The resulting cellulose ethers have
    The following characteristics are given in Tables-4. The results show that the viscosity drastically increases G by increasing the molecular hydroxybutyl substitution, and a significant improvement in the transparency of the fiber content is obtained by increasing the hydroxybutyl substitution. The high level of viscosity, the relative low transparency and the high fiber content are due to the fact that the paper pulp used as the starting material has a low reactivity. Examples 24 and 25. Sheet acetate cellulose type (SP 1000) is mercerized for 30 minutes at room temperature in a 20% aqueous solution of sodium hydroxide, after which the mass is squeezed to a degree of extraction of 2.5 and crushed by grinding. In the reactor load ground cellulose in the amount of 2.5 May. h. together with 1.5 May. including ethyl chloride, 0.25 May. including ethylene oxide and 1.1 May. including propylene oxide. Thereafter, the temperature is continuously stirred for 30 minutes and maintained at this level for 3 hours. The reaction is stopped and the remaining ethyl chloride is removed, after which the cellulose ether is washed, neutralized, dried, dried and crushed. To a friend | Part of the cellulose ether is obtained in a similar way, except that after the reaction, carried out at 70 ° C, the temperature is raised to 105 ° C in 25 minutes and maintained at this level for 75 minutes. Thereafter, the reaction is stopped and the ethyl chloride present is removed from the reaction zone. Next, the resulting cellulose ether is treated as described above. The cellulose ethers have the following characteristics, given in table. five.
    13
    MOH
    GMD YUHSIETIL
    MZL MLA |) OKS "PROPI
    Ethyl Viscosity, cps
    transparency,% Fiber content,% Temperature of the photocell, Cellulose ether with C3, 0.4 has a higher viscosity than cellulose ether with C3, | yl 0.25, although it has more hydrophobic groups than the compared product, and it is treated at 105 ° C for 75 minutes, which in itself promotes the degradation of the cellulose ether and, therefore, its viscosity decrease. Examples 26 and 27. Similar GIDgroksiA
    hydroxyl proPIA 9TIL
    Viscosity, cp transparency,% Content of BohoKHa,% Temperature of focculation,
    1105118
    14 Table. five
    0.5
    1.5
    0.40
    1540
    96.0
    ABOUT
    52
    Table 6
    1,3
    0.5
    0.25
    2750
    99.7
    ABOUT
    62 but examples 23 and 24 receive two different cellulose ethers by treating one cellulose ether at elevated temperatures (in accordance with Example 24), except that ethylene oxide and propylene oxide are loaded in quantities of 0.6 and 0.4 May, h respectively on May 1. including dry pulp. Get the following results (table. 6). Cellulose ether, which has a higher ethyl substitution, has a significantly higher viscosity than the comparable product. Examples 28-30. 1 mah. acetate mass in accordance with example 1 mercerized 6 for 30 min 20% -n | aqueous solution of sodium hydroxide at room temperature, wring out to a wring degree of 2.5 and crushed. Then, crushed alkali cellulose together with 1.5 May is loaded into the reactor. including alkyl chloride, 0.3 May. including oxide 1816 ethylene and 1.4 May. including propylene oxide. The kind of alkyl chloride varies in the three examples and is ethnyl chloride, propyl chloride and butyl chloride. Three hours after the reaction at 70 ° C, the temperature was raised to 105 ° C in 25 minutes and maintained at this level for 3 75 minutes, after which the chlorine alkyl was removed from the reactor, and the resulting cellulose ether was subjected to further processing. Get the following results, summarized in table. 7. Table 7
    权利要求:
    Claims (1)
    [1]
    . METHOD FOR PRODUCING MIXED SIMPLE CELLULOSE ETHERS by treating mercerized cellulose with esterifying agents followed by washing and drying the target product, characterized in that, in order to obtain esters with a reduced flocculation temperature with increased hydrophilicity, the treatment is carried out on May 0.2-10. including alkyl chloride C 2 -C ^, 0.025-0.82 may. including ethylene oxide, 0.4-1.4 may. including propylene oxide and / or 0.089-0.9 may. including butylene oxide. on May 1. including cellulose to a degree of substitution with alkyl of 0.1-0.8, ethyl 0.5-1.5, hydroxypropyl 0.5-2.0 and / or hydroxybutyl 0.1-1.0.
    类似技术:
    公开号 | 公开日 | 专利标题
    SU1105118A3|1984-07-23|Method of obtaining cellulose mixed ethers
    US2517577A|1950-08-08|Preparation of carboxyalkyl ethers of cellulose
    US6686464B1|2004-02-03|Cellulose ethers and method of preparing the same
    US20050250940A1|2005-11-10|Cellulose ethers and method of preparing the same
    US4990609A|1991-02-05|Sulfoethyl cellulose of high solution quality and a process for its production
    US2744894A|1956-05-08|Hydroxyalkylation of polysaccharides
    US2572039A|1951-10-23|Manufacture of cellulose ethers
    US4399275A|1983-08-16|Preparation of highly reactive cellulose
    US2332048A|1943-10-19|Preparation of water-soluble carboxyethyl cellulose ether
    US2349797A|1944-05-30|Alkali-soluble carboxyethyl cellulose ether
    US1884629A|1932-10-25|Treatment of cellulose and derivatives thereof
    US4480091A|1984-10-30|Process for preparing cellulose sulfate esters
    US5294702A|1994-03-15|Water-soluble polymerizable 3-allyloxy-2-hydroxypropylether of cellulose
    US2148952A|1939-02-28|Process for preparing cellulose ethers and products
    US2173471A|1939-09-19|Hydroxyalkylation of celluloses
    US6835828B2|2004-12-28|Alkylene oxide modified hardwood cellulose
    US3536697A|1970-10-27|Process for improving the processability of refined cellulose pulp
    US2131733A|1938-10-04|Cellulose derivatives
    US3549617A|1970-12-22|Brightening water-soluble cellulose derivatives
    US1876920A|1932-09-13|Manufacture of carbohydrate derivatives
    US2172109A|1939-09-05|Alkali soluble cellulose ethers
    US2265919A|1941-12-09|Treatment of alkali soluble cellulose ethers
    FI67860C|1985-06-10|PHOSPHONMETHYLSUBSTITUENT INNEHAOLLANDE VATTENLOESLIGA CELLULOSABLANDETRAR OCH FOERFARANDE FOER FRAMSTAELLNING AV DEM
    US2173470A|1939-09-19|Hydroxyalkylation of cellulose and derivatives
    GB343521A|1931-02-20|Improvements in or relating to the manufacture of cellulose ethers
    同族专利:
    公开号 | 公开日
    DE2412014C3|1979-03-15|
    IE38897L|1974-09-14|
    NO137278C|1978-02-01|
    NL7403267A|1974-09-17|
    ATA210374A|1975-08-15|
    DE2412014A1|1974-10-03|
    CS228901B2|1984-05-14|
    US3926951A|1975-12-16|
    BE812233A|1974-07-01|
    FR2221463B1|1976-12-17|
    SE403782B|1978-09-04|
    GB1453382A|1976-10-20|
    DD112275A5|1975-04-05|
    JPS5328190B2|1978-08-12|
    FI56847B|1979-12-31|
    IT1009296B|1976-12-10|
    NL162660B|1980-01-15|
    NO137278B|1977-10-24|
    CA1010857A|1977-05-24|
    FR2221463A1|1974-10-11|
    CH614220A5|1979-11-15|
    FI56847C|1980-04-10|
    PL89900B1|1976-12-31|
    NL162660C|1980-06-16|
    IE38897B1|1978-06-21|
    DE2412014B2|1978-07-13|
    NO740811L|1974-09-17|
    JPS49128084A|1974-12-07|
    AT329589B|1976-05-25|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US2839419A|1956-07-11|1958-06-17|Dow Chemical Co|Water-soluble thermoplastic cellulose ether compositions|
    US2965508A|1958-05-13|1960-12-20|Dow Chemical Co|Water soluble thermoplastic cellulose ether compositions|
    US3296247A|1964-07-06|1967-01-03|Hercules Inc|Mixed cellulose ethers|
    GB1144225A|1965-09-07|1969-03-05|Dow Chemical Co|Preparation of medicinal capsule shells from hydroxyalkyl-alkyl cellulose ethers|
    JPS4819233B1|1970-04-27|1973-06-12|
    US3873518A|1973-12-14|1975-03-25|Dow Chemical Co|Water soluble ternary cellulose ethers|US4096325A|1976-02-20|1978-06-20|Anheuser-Busch, Incorporated|Methyl hydroxypropyl cellulose ethers|
    US4096326A|1976-10-13|1978-06-20|Hercules Incorporated|Dihydroxypropyl cellulose|
    US4341563A|1978-11-17|1982-07-27|Sankyo Company Limited|Protective coating compositions|
    US4458068A|1983-03-25|1984-07-03|The Dow Chemical Company|Water-soluble, ternary cellulose ethers|
    US5728437A|1987-08-26|1998-03-17|Astra Meditec Aktiebolag|Articles exhibiting a blood-compatible surface layer and process for providing articles with such a surface layer|
    SE500783C2|1992-05-05|1994-09-05|Eka Nobel Ab|Ways to clean wood resin-containing process or wastewater|
    ES2162638T3|1994-08-30|2002-01-01|Alcon Lab Inc|SUPPLY VEHICLES OF PHARMACOS WITH THERMAL GELIFICATION CONTAINING ETERES OF CELLULOSE.|
    SE503765C2|1994-12-15|1996-08-26|Akzo Nobel Nv|Process for preparing a suspension in water of a cellulose ether and dry mixture suitable for use in the preparation of the suspension|
    US5770528A|1996-12-31|1998-06-23|Kimberly-Clark Worldwide, Inc.|Methylated hydroxypropylcellulose and temperature responsive products made therefrom|
    US5969052A|1996-12-31|1999-10-19|Kimberly Clark Worldwide, Inc.|Temperature sensitive polymers and water-dispersible products containing the polymers|
    US5986004A|1997-03-17|1999-11-16|Kimberly-Clark Worldwide, Inc.|Ion sensitive polymeric materials|
    US6043317A|1997-05-23|2000-03-28|Kimberly-Clark Worldwide, Inc.|Ion sensitive binder for fibrous materials|
    US5976694A|1997-10-03|1999-11-02|Kimberly-Clark Worldwide, Inc.|Water-sensitive compositions for improved processability|
    US6423804B1|1998-12-31|2002-07-23|Kimberly-Clark Worldwide, Inc.|Ion-sensitive hard water dispersible polymers and applications therefor|
    US6686464B1|1999-04-26|2004-02-03|Bki Holding Corporation|Cellulose ethers and method of preparing the same|
    CN1239780C|1999-04-26|2006-02-01|Bki控股公司|Cellulose ethers and method of preparing same|
    US6653406B1|2000-05-04|2003-11-25|Kimberly Clark Worldwide, Inc.|Ion-sensitive, water-dispersible polymers, a method of making same and items using same|
    US6835678B2|2000-05-04|2004-12-28|Kimberly-Clark Worldwide, Inc.|Ion sensitive, water-dispersible fabrics, a method of making same and items using same|
    US7101612B2|2000-05-04|2006-09-05|Kimberly Clark Worldwide, Inc.|Pre-moistened wipe product|
    US6548592B1|2000-05-04|2003-04-15|Kimberly-Clark Worldwide, Inc.|Ion-sensitive, water-dispersible polymers, a method of making same and items using same|
    US6815502B1|2000-05-04|2004-11-09|Kimberly-Clark Worldwide, Inc.|Ion-sensitive, water-dispersable polymers, a method of making same and items using same|
    US6713414B1|2000-05-04|2004-03-30|Kimberly-Clark Worldwide, Inc.|Ion-sensitive, water-dispersible polymers, a method of making same and items using same|
    US7276459B1|2000-05-04|2007-10-02|Kimberly-Clark Worldwide, Inc.|Ion-sensitive, water-dispersible polymers, a method of making same and items using same|
    US6599848B1|2000-05-04|2003-07-29|Kimberly-Clark Worldwide, Inc.|Ion-sensitive, water-dispersible polymers, a method of making same and items using same|
    US6429261B1|2000-05-04|2002-08-06|Kimberly-Clark Worldwide, Inc.|Ion-sensitive, water-dispersible polymers, a method of making same and items using same|
    US6683143B1|2000-05-04|2004-01-27|Kimberly Clark Worldwide, Inc.|Ion-sensitive, water-dispersible polymers, a method of making same and items using same|
    US6579570B1|2000-05-04|2003-06-17|Kimberly-Clark Worldwide, Inc.|Ion-sensitive, water-dispersible polymers, a method of making same and items using same|
    US6444214B1|2000-05-04|2002-09-03|Kimberly-Clark Worldwide, Inc.|Ion-sensitive, water-dispersible polymers, a method of making same and items using same|
    BR0115388A|2000-11-01|2005-01-04|Bki Holding Corp|cellulose ethers and method of preparation thereof|
    US6828014B2|2001-03-22|2004-12-07|Kimberly-Clark Worldwide, Inc.|Water-dispersible, cationic polymers, a method of making same and items using same|
    US6897168B2|2001-03-22|2005-05-24|Kimberly-Clark Worldwide, Inc.|Water-dispersible, cationic polymers, a method of making same and items using same|
    US7070854B2|2001-03-22|2006-07-04|Kimberly-Clark Worldwide, Inc.|Water-dispersible, cationic polymers, a method of making same and items using same|
    US6908966B2|2001-03-22|2005-06-21|Kimberly-Clark Worldwide, Inc.|Water-dispersible, cationic polymers, a method of making same and items using same|
    WO2007056070A2|2005-11-04|2007-05-18|Hercules Incorporated|Ether derivatives of raw cotton linters for water-borne coatings|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    SE7303582A|SE403782B|1973-03-14|1973-03-14|NONJONIC CELLULOSEETERS|
    [返回顶部]