• 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:
    Process for preparing block copolymer involves dry blending salt of a prepolyamide, e.g. a 30203-6 salt, and particules of melt-spinnable polyamide. Blend is heated to a temperature in the range of between from the melting point of higher melting component to below amide-interchange temperature of a blend of the melt-spinnable polyamide and the homopolymer which would result from the polymerization of the salt. Heating and mixing are continued until substantially all of the salt and the polyamide are converted into a block copolymer. The latter can be used to make fibers.
    公开号:SU805951A3
    申请号:SU772541254
    申请日:1977-11-04
    公开日:1981-02-15
    发明作者:Л.Никол Стефен
    申请人:Сантек Инк (Фирма)；
    IPC主号:
    专利说明:

    (54) METHOD OF OBTAINING POLYAMIDE BLOCK COPOLYMER
    One of the components used in the proposed method as a starting material is
    R.
    / G- i nY —Hr- y (, —C — C —C — CH —H N) oC — Rj — C — S ———,
    HR, where the radicals R, R and Rj are selected from the group containing hydrogen, () -alkyls and (Cj- (1d) -isoalkyls; the radical R is selected from the group containing () -alkylenes and (C dizo alkylenes; radical R. is selected from the group containing Cg-arylenes (Cp-C-alkylene and G-isoalkylenes. The above solid salt can be considered as a prepolymer polyamide, because when heated under suitable conditions, the salt loses water and forms a group of the formula -NH-CO-, characteristic of polyamide. Another component used in the proposed method as a starting material is straight polyamide in the melt. The term polyamide in the melt excludes polyamide, which can be formed from the aforementioned salt of the pre-polymer polyamide. Plasma polyamides can be melted, in which the difference between the melting point and the decomposition temperature of the molten polymer is at least. Pred: 1: Lx polyamides are the following polymers: nylon-6, also known as polyhexamethylene adipamide; nylon 6, 10 (polyhexamethylene sebacamide); nylon b (polypentamethylene carbonamide); nylon-11 (polydecamethylenecarbonamide MHD-6 (polymethoxypropylene) known polymers. The ratio of salt to amount / molten polyamide can vary within wide limits. If a large amount of any of the components is used, the copolymer obtained will not be a copolymer, but a copolymer containing -pH. CHji-C- Ci-OR Ch. -OS1 -d - bNgII I t H Zhz - RjH where all radicals R is as defined above and denotes the relative amounts of each component present. Thus, the percentage of ti / (MM) (100) in the working range is a salt selected from the group containing prepolymer polyamides of the following formula
     S
    Rj H is predominantly long chains of the prevailing component with bridges of relatively short segments of the smaller component arranged in a statistically disordered manner. Differences between non-ordered and block copolymers can be determined by comparing the physical properties of these polymers. The working range of the ratio of salt to total weight of the components is from 10 to about. 75 wt.%, Preferably 20-40 wt.%. The method involves dry mixing the dry salt of a prepolymer polyamide with dry particles or in a polyamide melt. Then the resulting mixture is heated in an inert atmosphere. The temperature of the mixture is in the range from the melting point of the high-melting component of the mixture to the approximate temperature at which the polyamide and polyamide mixture formed in the melt, resulting from the polymerization of the salt, is transamidated. The lower temperature limit is determined by the melting point of either the molten polyamide or the salt, depending on which melting point is higher. The upper limit of the temperature for the proposed method is the reamidation temperature. The heated mixture of salt and molten polyamide is mixed at the above temperature and in an inert atmosphere. Mixing at elevated temperature is continued until complete conversion of the entire salt and polyamide into a block polymer. During the process, samples of the mixture can be sampled and subjected to testing for substantial completeness of conversion. After the whole salt and polyamide are converted into a block copolymer, the resulting copolymer has the following structure J 1 I A8yxSa. & ntpnyi E c-Q 4 - paduHOfl / p omogo LLV pacr, a8e no / ttjaOJ, at least 10-75 wt.%. In the polyamide melt, nominal amounts of unreacted salt or direct may remain. However, their effect on the properties of the resulting block copolymer is insignificant. In addition, any
    the reacted component may be G1-vrg11 in the subsequent processing of the block copolymer, for example, when converting it into a fiber. On the other hand, stonds (ciHz) .j-o- {ciHz) j-o- (eHt) jiiH5 p-6- (dHz) -c; -about ,
    which can be considered salt 30203-6. This salt is prepared as follows.
    First, 1.2-6c (beta-cyanoethoxyethane) of the following structure is obtained: NC- (CH2.), 2.-0 (CH2) 2.-0- (CH ,, -CN. To obtain it in a 5-liter glass A double-walled reactor (for cooling with water), equipped with a shut-off valve and going to the bottom of the tube, is loaded with 930 r, (l5 mol) ethylene glycol and 45.6 g of a .40% aqueous solution of potassium hydroxide. 1620 g (30.6 mol of acrylonitrile (CN-CHsCH)) at such a rate that its temperature was below 35 ° C. and after stirring is complete, the mixture is stirred for an hour and then left The mixture is neutralized to pH 7 by adding 6 M hydrochloric acid solution. After washing three times with a saturated solution of sodium chloride, the product is separated from the aqueous layer, dried over calcium chloride and passed through an alumina column to completely remove all the basic substances. em 90% of theoretical.
    At the next stage, 4.7 dioxadecamethylenediamine of the formula NHi (CH2L) 2.-0- (CHi) -0- (CH2) (CH2), j-NH .B of 800 ml reactor with a capacity of 800 ml is charged with 150 g of 1,2-bis- (beta). -cyanoethoxyethane), 230 ml of dioxane and about 50 g of Rene cobalt. After blowing air into the reactor, hydrogen is supplied under a pressure of 2000 pounds from KB in. (130.6 kg / cm) and heated to -. Due to the consumption of hydrogen, an additional amount of hydrogen is added, while the pressure is constant. After cooling, the pressure is removed and the catalyst is filtered off. Dioxane was removed by distillation at atmospheric pressure. The residual mixture is distilled using a distillation apparatus equipped with a 3 ft long coil.
    11 -R,
    to, to. Of. 1 1, t CH-C-C-O-R.-O-C-C-CH-n NJ
    and IIII 13 / H R. R, M is hydrogen, (Cj - - 0 where R, R.2, R is alkyl, C is IEO-alkyl) - (C. (5) -alkylene, 2, -isoalkiones, it can be removed by various means.
    . Example. Salt of the following structure is used as a component.
    (0.91 m). The diamino compounds are distilled off at 123-124 ci under pressure.
    0 3.75 mm Hg Get about 98 g of material with a purity of 99.95%. The resulting product is considered diamine 30203.
    At the next stage, the salt is obtained. To a solution of 41.5 g of adipic acid, dissolved in a mixture of 250 ml of isopropanol and 50 M.I ethanol, is added with stirring 50 g of diamine 30203 dissolved in 200 ml of isopropanol. An exotherm occurs. Salt is collected on water.
    The Buchner bottle is then recrystallized from 400 MJJ ethanol to 300 ml isopropanol. Vacuum dried product overnight
    5 at 60 ° C has a melting point of 127-128 ° CjpH of a solution of 6.9. Obtain 85 g of salt (yield 92% of theoretical).
    A block copolymer was prepared as follows.
    0 way.
    17.1 g of dry salt 30203-6 and 40 g of dry milled nylon-6 are mixed in a dry state in a suitable container using a ball mill. After mixing, the mixture is introduced into a container equipped with a stirrer. The container and its contents are rinsed with dry nitrogen. The tank is inserted into a steam bath, in which it is under. the temperature is kept at 245 ° C and the pressure is given a positive nitrogen pressure.
    From the moment of melting of the mixture, it is stirred for 1 hour. After cooling, the resulting block copolymer is analyzed for its structure.
    权利要求:
    Claims (1)
    [1]
    5 claims
    The method of producing a block copolymer of polyamides by the reaction of transamidation of a melt-injected polyamide, characterized by
    For this purpose, in order to simplify the process, dry salt is added to the polyamide in the form of dry solid particles or in the melt in an amount of 10-75 wt.% To the total weight of the components.
    0 r 1
    ft, v
    - M (I GOC-R-CO and MO Rg- - (Sat-C, 4) -arylene, (GO) -alkylene, (Cj-C ,,) -isoalkiol that H - the mixture is stirred in an inert atmosphere at a temperature and interval
    7 8059518
    melting points high melting sources of information
    the components and temperatures of the transamide are taken into account in the examination of vanilla melt mixtures - 1. US Patent No. 3683047,.
    Lyamida and polyamide, which is semi-cl. 260 - 857, published. (protochavts as a result of the polymerization of salt. type).
    类似技术:
    公开号 | 公开日 | 专利标题
    CA1052941A|1979-04-17|Manufacture of polyamides
    SU805951A3|1981-02-15|Method of preparing polyamide blockcopolymer
    KR100484572B1|2005-04-20|Process for the anionic polymerization of lactams
    EP0227866A1|1987-07-08|Catalytic process for the preparation of polyamides from omega - aminonitriles
    US4360646A|1982-11-23|Preparation of lysine based macromolecular highly branched homogeneous compound
    Lyman et al.1959|Interfacial polycondensation. XI. Ordered copolymers
    CA1155585A|1983-10-18|Manufacture of a block copolymer containing apolyetheramide and a polylactam
    US4219636A|1980-08-26|Preparation polyamides of isophthalic acid and hexamethylene diamine with formic acid
    CA1090033A|1980-11-18|Single step preparation of block copolymer of polyamides
    Qin et al.1985|Synthesis and characterization of model urethane compounds
    Podkoscielny et al.1984|Linear polythioesters. VII. Products of interfacial polycondensation of 1, 4‐di |‐2, 3, 5, 6‐tetramethylbenzene with some aliphatic acid dichlorides
    Stehlíček et al.1991|On the synthesis of poly |—poly | block copolymers for the reaction injection molding process
    EP1274767B1|2012-10-31|Process for the simultaneous preparation of polyamides with at least two different viscosities
    US4804753A|1989-02-14|Process for the preparation of Schiff's bases
    Chu et al.1986|Nucleic acid base grafted polyethylenimine. Cytosyl pendant groups synthesis and characterization
    Trivedi et al.1980|Synthesis and properties of poly |
    KR0171611B1|1999-05-01|Copolymer of dodecane terephthalamide
    US3830786A|1974-08-20|Process for the production of basic polyamides and copolyamides
    Özgün et al.1986|Synthesis of block copolymers based on polycaprolactam-polybutadiene
    Podkoscielny et al.1981|Linear polythioesters. V. Products of interfacial polycondensation of 4, 4′‐di |‐benzophenone with some aliphatic acid dichlorides
    Macdonald et al.1973|Condensation polymers from 1, 2, 5‐thiadiazole‐3, 4‐dicarboxylic acid
    SE447733B|1986-12-08|SEGMENT POLYMERS OF POLYETERAMIDE AND SLOPE POLYMERS OF POLYAMIDE AND POLYETERAMIDE AND PROCEDURE FOR PREPARING THE SEGMENT POLYMER
    EP0053934A1|1982-06-16|Process for the preparation of polyamides
    Perez‐Camacho et al.1997|Preparation of hydroxyl‐functionalized SEBS for in situ graft reaction compatibilizing agents
    US3767686A|1973-10-23|Halogenated diamino diphenyl sulfone derivatives
    同族专利:
    公开号 | 公开日
    US4045511A|1977-08-30|
    IT1088029B|1985-06-04|
    FR2370068B1|1983-10-21|
    FR2370068A1|1978-06-02|
    NL7712223A|1978-05-10|
    DK496277A|1978-05-09|
    CA1090032A|1980-11-18|
    BE860586A|1978-05-08|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US2577621A|1948-08-03|1951-12-04|May Geoffrey Bilson|Production of polyamides of high molecular weight utilizing 1:4-bis--cyclohexane|
    DE1520933B2|1964-05-23|1974-05-09|Schering Ag|Process for the production of copolyamides and their use as hot-melt adhesives|
    US3397107A|1965-07-22|1968-08-13|Kanegafuchi Spinning Co Ltd|Composite polyamide filaments with improved potential crimpability and method of making the same|
    GB1180403A|1966-02-11|1970-02-04|Toyo Rayon Co Ltd|Polyamide Resin Composition|
    GB1169276A|1966-03-15|1969-11-05|Toyo Boseki|A process for the production of Polyamides having improved Hydrophylic Properties|
    DE1720217A1|1966-06-22|1970-06-04|Asahi Chemical Ind|Process for making block copolymers|
    DE1595758A1|1966-08-02|1970-02-12|Glanzstoff Ag|Process for the production of polyamides with Aether bonds|
    US3729449A|1969-08-27|1973-04-24|Kanegafuchi Spinning Co Ltd|Polyamide fibers composed of the polyamide and methods for producing thereof|
    US3863609A|1972-09-19|1975-02-04|Yoshio Ikarashi|Rotary engine|
    US3882090A|1973-06-04|1975-05-06|Eastman Kodak Co|Water-soluble polyamides from alkyleneoxy bis|
    IN142629B|1973-11-14|1977-08-06|Sun Ventures Inc|
    US4044071A|1976-11-08|1977-08-23|Suntech, Inc.|Single step preparation of block copolymer of polyamides|US4044071A|1976-11-08|1977-08-23|Suntech, Inc.|Single step preparation of block copolymer of polyamides|
    US4165346A|1976-11-26|1979-08-21|Sun Oil Company Of Pennsylvania|Copolymer of poly-polycaprolactam containing terephthalic acid|
    US4235714A|1978-12-18|1980-11-25|Suntech, Inc.|Hydrophilic polyamide film for semipermeable membranes|
    US4273898A|1979-09-06|1981-06-16|Suntech, Inc.|Block copolymer of polyetheramide and random copolymer of polyamide and polyetheramide|
    US4297454A|1979-11-14|1981-10-27|Suntech, Inc.|Manufacture of a block copolymer containing a polyetheramide and a polylactam|
    US4328331A|1981-04-20|1982-05-04|The Upjohn Company|Novel polyester-amides|
    US5030710A|1990-04-10|1991-07-09|Texaco Chemical Company|Nylon-6 modified with low molecular weight polyethylene glycol diamines|
    US5330834A|1992-05-12|1994-07-19|E. I. Du Pont De Nemours And Company|Dye-retarded nylon 6/6,6 block copolymer fibers|
    US5254668A|1992-06-29|1993-10-19|Texaco Chemical Company|Polyamidopolyfunctional amine from lactam and ether amine|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    US05/740,159|US4045511A|1976-11-08|1976-11-08|Minimum energy process for preparing block copolymers of polyamides|
    [返回顶部]