• 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:
    1469349 Flame retardant polyesters HOECHST AG 16 Sept 1974 [17 Sept 1973] 40280/74 Heading C3R A flame retardant linear polyester is derived from a dicarboxylic acid, a diol and from 3 to 20 mol. per cent, based on the total acid components, of a carboxyphosphoric acid of the formula in which R is a saturated cyclic or acyclic alkylene radical, an arylene radical or an aralkylene radical and R 1 is a C 1-6 alkyl group, an aryl group or an aralkyl group, or an ester or cyclic anhydride thereof. The polyester preferably contains at least 0À5 weight per cent of phosphorus. The polyester may contain fibres of glass, quartz, asbestos or carbon. The examples describe preparing polyesters from dimethyl terephthalate, optionally with di-methyl isophthalate, ethylene glycol and various phosphinic compounds of the above formula, e.g. 2 - carboxy - ethyl - methylphosphinic acid and 2 - methyl - 2,5 - dioxo - 1 - oxa - 2 - phospholane having the formula
    公开号:SU850010A3
    申请号:SU742060555
    申请日:1974-09-13
    公开日:1981-07-23
    发明作者:Кляйнер Ханс-Ерг；Финке Манфред；Боллерт Ульрих；Хервиг Вальтер
    申请人:Хехст Аг (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to methods for producing linear polyesters modified with carboxyphosphinic acids. Methods are known for producing linear polyesters by reacting dicarboxylic acids or their esters with diols and with various phosphorus compounds capable of incorporating into polyether molecules, for example, GL and 2 phosphonic acids and phosphinic acids, V have known methods that have improved twisting fibers and fibers based on such polyesters However, the phosphorus introduced into the polyester does not provide sufficient flame-retardant properties, since it is introduced in too small an amount (0.1-1.0 wt.%). A higher phosphorus content leads to an undesirable fragility of the material. To achieve sufficient and good flame-retardant properties, a higher phosphorus content of at least 1 wt.% Is necessary. In addition, the polycondensation step in the production of polyester is carried out with mainly at high temperatures. At these temperatures, of esters of phosphoric acids and esters formed polialkilenfosfornyh acid by thermal cleavage of a very small amount of free phosphoric acid, which causes during the polycondensation substantial formation of diglycol, and polyesters polychao vle using esters of phosphoric or polialkilenfosfornyh acids contain very significant amount diglycols. Due to this, the melting point of the polyester is reduced and the other properties of the polyesters are adversely affected. Polyesters; obtained according to these methods with the addition of esters of phosphoric and / or polyphosphoric acids, are also not thermally stable, and may have a low flammability. copolyesters containing phosphonic acids, which are non-flammable and heat resistant, are also known and can be used as flame retardant impregnating and adhesive agents, varnishes and impregnating agents for paper and textiles, as well as intermediate products, to form them into yarns and fibers, however, it is not possible, since a high phosphorus content causes brittleness of the products. Low flammability polyesters are also obtained by incorporating phosphorous compounds that are not embedded in polymers into the polyester. As such additives, for example, phosphate esters of halogen-containing aromatic dihydroxy compounds, polyphosphonates and poly (phosphonate phosphates) Gz are used.
    However, such additive substances. have a significant migration capacity of additives in the polymer & x, which causes, on the other hand, the toxicity of the corresponding polymer products, and on the other, the relatively easy removal of additives during, for example, dry cleaning of the corresponding fiber products. Due to the leaching of the additive materials, the polymeric products lose their reduced flammability and result in an undesirably high content of diglycols, as they are added during the formation of polyesters.
    Compared to polymers, in chain molecules of which phosphorous compounds are included, polymers containing the corresponding additive substances are less paintable.
    The closest to the proposed invention in its technical essence is a method for producing linear polyethers (polyethylene terephane) by reacting dicarboxylic acids or their esters with diols and with bis (p-carboxyphenyl) phosphinic acid to improve the dyeability of f4 polyesters,
    However, bis- (p-carboxyphenyl) -phosphonic acid is a trifunctional compound, which can lead to undesirable cross-linking of polymer chains. Because of the functionality of the bis (p-carboxyphenyl) phosphonic acid and; the resulting crosslinking effect, the compound is not added to the batch to form a polyester, but is first treated with a diol in the presence of an alkali metal cyanate or alkali metal cyanate. from functional groups.
    IF this treatment is not carried out prior to the addition of the modifier to the loading material to form a polyester, t.e. if bis- (p-carboxyphenyl) phosphinic acid is used directly for condensation with a polyester, then polyether is not suitable for use.
    The purpose of the invention is to obtain flame-retardant polyesters with good dyeability, possessing high heat resistance.
    This goal is achieved by using 3-20 mol.% Of the total amount of acid components of carboxyphosphinic acids as phosphorus compounds capable of incorporation into the polyester molecules.
    formulas
    ABOUT
    IO-R-UNHA,
    .
    where r
    saturated linear or cyclic alkylene, arylene, aralkylene;
    R. alkyl with 1-6 carbon atoms, aryl or aralki and both R and R may contain one or more heteroatoms, preferably F, C & , V g, O and S, or esters of these acids and lower aliphatic alcohols, or cyclic anhydrides of these acids.
    Heteroatoms can be in both the side chain and the main chain, with a preferred position in the main chain. This position means that the heteroatom is an element consisting of C-atoms of the chain, because of the univalence of hygiene they are not applicable in this case. In the first place, the atom of oxygen and sulfur is taken into account as chain links. M-atoms, which in the form of -NH- or NR-rpynn (R-alkyl) can also be such units, are less preferred, since N-compounds often cause undesirable staining.
    The atoms in the chain can be in the form
    ABOUT
    V
    and.
    -S-, -S-, or -S- groups, and in the lateral position or in the aromatic ring, preferably in the form of -SOa H, (Na) -groups.
    If R is a linear or cyclic alkylene residue, then transfer to halogen should be taken into account only when these compounds, under the conditions of polyether production, do not release hydrogen hydrogen or only insignificantly.
    Suitable halogen-substituted alkylene residues are, for example, the residue
    -sn -sn -sn -, -,
    . Chjx
    where X FjCfc, Br or perfluorinated alkyles-bstatki.
    The residue may contain heteroatoNbi, and the substituents may be halogen atoms and SOj Na-rpynпа, for example, the groups C, H /, Sv, C HiiSOjNa and others. Linear polyethers containing certain structural units as links, receive as follows. Common starting materials are converted in a known manner, suitable for producing high molecular weight, especially fiber and film-forming, linear polyesters, and before the process during the polycondensation process or long before the end of the polycondensation, bifunctional carotid hydroxyphosphinic acids containing other heteroatoms are added, and / or their esters of lower aliphatic alcohols with the number of C-atoms from 1 to 4 or the same diol, which is a component of the polyester. Carboxyphosphinic acid-diol ether oligomers can also be used. Cyclic anhydrides of carboxyphosphinic acids, which are easily formed and well accessible, are also possible. The amount of carboxyl phosphinic acid should be 3–20 mol% of the total amount of acid components. Carboxyphosphinic acids correspond to the formula HO-P-TJ-COOH, where R and R have the above meaning. I Dicarboxylic starting materials are used in the form of free acids or their esters of lower aliphatic alcohols, preferably with 1-4 C-atoms, in addition to terephthalic acid, also other dicarboxylic acids, mainly as co-components. Following mentioned, for example, isophthalic acid, 5-sulfoisophthalic acid, 5-sulfopropoksi-isophthalic acid of naphthalene-2, b-dicarboxylic acid, biphenyl, n, n-dicarboxylic acid, p-phenylene diacetic acid, p-phenylene oxide, p dicarboxylic acid, diphenoxyapan-dicarboxylic acids trans-hexahydro-terephthalic acids, adipic acid, sebacic acid, 1,2-cyclobutane-dicarboxylic acid, etc. higher homologues of butanediol 1,4, further 2,2dimeti l-propandiol-1, 3,1,4-diclohec sandymethanol and others, also as co-components. In addition to terephthalic acid, they use Diconovic acids in an amount of not more than 10 mol%. In a similar manner, the composition of the diol component is obtained If, in addition to ethylene glycol, other diols are used as a co-component, their amount is not more than 10 mol.% Of the total diol volume. Free dicarboxylic acids and diols are first converted, as is the case with these reaction components, to esters and then polycondensed. The esters of dicarboxylic acids, instead of free dicarboxylic acids, especially from dimethyl ethers, are first transesterified and then polycondensed using conventional catalysts. During the preparation of polyesters, besides catalysts, usual additives can also be added, for example crosslinking agents, matting agents, stabilizers, nucleating agents, dyes, fillers, etc. Bifunctional Carboxyphosphine added to the process during polycondensation or shortly before the end of polycondensation acids, which may contain other heteroatoms, or their esters or cyclic anhydrides, are prepared by known methods. Carboxyphosphinic acids and their esters or cyclic anhydrides, in contrast to various diphosphinic acids, are non-volatile under the conditions of polyester formation and, therefore, are fully and well embedded by condensation. In the final polyester product, an organophosphate structural unit is statically distributed over the macromolecule. Due to the static distribution, the unit of carboxyphosphinic acid can also be in the form of a terminal group. In order to provide the desired reduced inflammability for the molding materials, the phosphorus content in the polyester needs to be at least 0.5 wt.% And about 1 wt.% In fibers and filaments. Ignited e-. pony bridge) (when phosphorous units contain halogen as a heteroatom. Polyesters are molded into fibers and threads, stretched and separated or extruded into films, or processed into molding products by extrusion, molding or extrusion. Particularly suitable are threads , fibers, films and moldings, which contain terephthalic acid as dicarboxylic acid, and ethylene glycol as diol. Fibers and filaments of the polyethers offered have excellent and constant non-flammability or IQpOMe then; 7O, they show a high degree of whiteness and are well colored with disperse dyes, and acid dyes - in medium or deep shades. When phosphorous units contain .Na-rpynnu, there is the possibility of dyeing The main dyes. The content of diglycol in polyesters is only slightly increased; the strength of fibers and filaments at break, glass transition temperature, melting point, etc. approximately correspond to the values that unmodified polyesters possess. Made from polyesters obtained by the proposed method, fibers and yarns are used in all those areas where it is impossible to use easily combustible textile and technical products, for example, for tarpaulins, carpets, curtains, etc. Filaments can be used together with other polymers as one of the components in two-component filaments. Films and molding products are used in all those areas where there is an increased risk of ignition. In molding products, when their transparency is not attached to values, in order to increase strength, inorganic fibrous materials, such as glass, quartz and carbon fibers, technical molding products, such as housings, structural electrical equipment, transfer details in machines, hollow housings, parts in computers and other sensitive electronic installations. A Example 1. 1000 g of dimethyl terephthalate under nitrogen and at a temperature of 170-220 C are transesterified with 720. ml of ethylene glycol in the presence of 230 mg of mg of sodium acetate tetrahydrate as a catalyst. At the end of the methanol cleavage, the 2-carbox ethyl methyl phosphine ciolot and etherification are added at 100 g. After the addition of 350 mg of Sbj0, the reaction vessel is heated, the pressure is reduced to 1 mm Hg. and the temperature is raised to. Polycondensation at 0.2 mm. Hg and continue until the relative viscosity is 1.85 (measured in 1% solution in dichloroacetic acid at). The temperature of the melting of the polycondensate is 244-248 C, the content of P is 1.85%. The polycondensate is molded under normal conditions from the melt and then drawn at a stretch ratio of 1: 3.65. The resulting yarns have a strength of 33 gf / tex at elongation, at break - 35%. The yarns are processed into the sleeved sleeve on which the dyeing and ignition tests are carried out. Acid dyeing with common names: Supranol is durable ;; :. red (C 1 24790), Alfan strong blue FGLL (C 1 62155) and pearl-barley yellow Lana E.G. (C 1 No. 19025) leads to deep shades. The flammability test is carried out according to the oxygen index method as per ASTM D 2863-70. At the same time, the sleeve is placed vertically in the apparatus and lit at the top. The oxygen content of the artificial environment of oxygen and nitrogen, in which the sample is only ignited, is determined. Found value of 29 vol.%. The corresponding sleeve of unmodified polyethylene terefleshat burns even when the oxygen content is 20% by volume. Example 2-8 (,. The experiment of Example 1 is repeated using other carboxy-phosphinic acids or derivatives introduced into polyether molecules. The results are shown in Table. Example 9. The experiment of Example 1 is repeated, replacing 6 mol.% Of dimethyl terephthalate dimethyl isophthalate during transesterification Polymer resin 236238 C, 4, f, 1.82. Drawing a hand from this material shows an oxygen index of 30%. Example 10. Example 1 is repeated, but instead of 100 g of 2-carboxyethylmethyl phosphinic acid, take 75 g of its cyclic anhydride 2-methyl-2, 5-dioxo-1-oxa-2-phospholane Formulas O he-R, instead of 350 mg, 300 microns GeHPOj. A pure white polyester containing 1.5% P was crushed in a cold state, / s 1.08 (measured in a mixture of phenol, tetrachloroethane 3: 3: 2 at 2S ° C.) Subsequent polycondensation in the solid state in a rotating vessel at and 0.2 mm Hg with a condensation time of 8 h / s (increase to 1.36). Granulate on the machine for casting pressure is molded into. tiles, the temperature of the cylinder is 250-270-260 s, and forNU is. Tiles of size 60x60x2 NW are transparent and completely colorless. j, s 1.25. Impact strength is tested by impact test. For this purpose, the tiles are subjected to shock load in such a way that the falling hammer is plumbly lowered from different heights to
    reinforced with PCIMKB tiles. The tip of the hammer pad is made in the form of a hemisphere with a radius of 10 mm. The weight of the hammer is 1 kg for each drop height. Test 10 tiles. With a given fall height, e.g. 150 cm, the impact energy is sufficient to break 50% of the tiles. The impact viscosity of tiles is 200 cm. Tiles obtained, ceteris paribus, only without the use of a phosphorous modifying compound with a / s 1.32, show the same test conditions for the impact strength of 190 cm.
    The test of flammability of granulates is formed at 230-250 ° and pressure 80 atm in tiles with a thickness of 1.3 mm. From these tiles chopsticks of size 127 12.7 mm are cut. When tested according to ASTHD 635-68, a non-flammable grade is obtained.
    Example I. Example 10 is repeated, but instead of 75 g, 35 g of 2-methyl-2,5-dioxo-1-oxa-2-phosphoana are added. The flammability test as per ASTM D 635-68 provides an assessment of self-extinguishing.
    The possibility of introducing large amounts of phosphorus without substantially degrading the properties of the polyester is a significant advantage over the known method.
    The polyesters obtained by the proposed method have excellent and permanent hard-to-resist or self-extinguishing properties, and also have good tinting ability, low diglycol content and good physicomechanical properties.
    The combination of excellent and permanent flame retardant properties and embellishment, which did not reduce the valuable properties of the unmodified linear polyester, was not observed in known polyesters modified with phosphorus compounds.
    0
    The proposed carboxyphosphinic acids or their derivatives are very well integrated into the linear polyester chain and have an optimal effect on the properties of this polyester (an optimal combination of poorly combustible or self-extinguishing properties and good dyeability with little or no deterioration in the valuable properties of the unmodified proliferator).
    90
    100
    1.98 241-245 1.6
    thirty
    1.54 243-245 1.25
    28
    1.87 241-243 1.4
    29

    si-p-he
    100
    1.81 247-249 1.4
    29
    but
    Cfchg
    125
    C, Hg-P-OH, j-CH, j-C-OOH 75
    权利要求:
    Claims (4)
    [1]
    1. For Germany 1520079,
    cl. 39v5, 17/015, published 1970.
    [2]
    2. For FEG 1595598,
    cl. 39 В®, 17/14, published D971.
    [3]
    3. The patent of France 1196971, cl. From 08 q, pub. 1959.
    [4]
    4. Patent FRG 1232348,
    39 s, 16, pub. 1967 (protokl
    type of) ,
    类似技术:
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    同族专利:
    公开号 | 公开日
    NL7412116A|1975-03-19|
    JPS5313479B2|1978-05-10|
    IT1021374B|1978-01-30|
    NO743328L|1975-04-14|
    ZA745811B|1975-09-24|
    IE40029L|1975-03-17|
    DK487074A|1975-05-12|
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    MY7800435A|1978-12-31|
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    DE2346787A1|1975-03-27|
    FR2243958B1|1979-02-16|
    HK58278A|1978-10-13|
    USRE30783E|1981-10-27|
    FI268574A|1975-03-18|
    BE820010A|1975-03-17|
    DK136158B|1977-08-22|
    DE2346787C3|1980-05-08|
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    CH571030A5|1975-12-31|
    FR2243958A1|1975-04-11|
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    DD120208A5|1976-06-05|
    DD114827A5|1975-08-20|
    CA1037194A|1978-08-22|
    LU70911A1|1976-08-19|
    GB1469349A|1977-04-06|
    US3941752A|1976-03-02|
    NL167180B|1981-06-16|
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    申请号 | 申请日 | 专利标题
    DE2346787A|DE2346787C3|1973-09-17|1973-09-17|Flame retardant linear polyesters, processes for their manufacture and their use|
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