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1.发明授权
公开(公告)号：US3994867A
公开(公告)日：1976-11-30
申请号：US537488
申请日：1974-12-30
CPC分类号： C08J3/00 , C08J2349/00 , Y10T428/3154
摘要： There are provided processes and compositions for obtaining organic polymeric materials having near-zero uniaxial thermal expansion coefficients. According to one embodiment, an organic polymer having a negative uniaxial thermal expansion coefficient is treated by thermal processing under conditions sufficient to cause at least a portion of the polymer chains to become misaligned, thereby decreasing the magnitude of this thermal expansion coefficient to nearly zero. According to a second embodiment, one or more organic polymers having a negative uniaxial thermal expansion coefficient are combined with one or more materials having a positive thermal expansion coefficient to yield a composite material having a uniaxial thermal expansion coefficient which is nearly zero.Useful in the practice of the invention are polyacetylenes having a negative macroscopic thermal expansion coefficient, which are obtained by the solid-state polymerization of crystalline monomers containing two or more conjugated acetylene groups.
摘要翻译： 提供了用于获得具有近零单轴热膨胀系数的有机聚合材料的方法和组合物。 根据一个实施方案，具有负单轴热膨胀系数的有机聚合物在足以使至少一部分聚合物链变得不对准的条件下通过热处理进行处理，从而将该热膨胀系数的大小减小到接近零。 根据第二实施方案，将具有负单轴热膨胀系数的一种或多种有机聚合物与具有正热膨胀系数的一种或多种材料组合，得到具有几乎为零的单轴热膨胀系数的复合材料。
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2.发明授权Metal complexed acetylenic compounds useful as environmental indicating materials 失效金属络合的炔属化合物可用作环境指示材料
公开(公告)号：US4788151A
公开(公告)日：1988-11-29
申请号：US912711
申请日：1986-09-29
IPC分类号： C07C275/20 , C07C275/28 , C07F1/00 , C07F3/00 , C07F19/00 , G01N31/22 , G01K11/16 , C07C127/15
CPC分类号： C07C275/28 , C07C275/20 , C07F1/005 , C07F19/005 , C07F3/003 , G01N31/22 , G01N31/222
摘要： Acetylenic complexes are disclosed that are useful as environmental indicating materials whereby exposure thereof to environmental stimuli induces a color change. These complexes contain at least one effective complexing metal and at least one acetylenic compound of the general formula:[R--(C"C).sub.a --(CH.sub.2).sub.b --(C"C).sub.c ].sub.2.dHXWherein a is 1 or 2, b is about 0-5; c is 0 or 1; with the proviso that when a is 1, b and c are 0, when a is 2, b is about 0-5 and c is 0 or 1; and R is --(CH.sub.2).sub.n -NHC(O)NHR'; wherein n is an integer of about 1 to 10; and R' is selected from the group consisting of: (a) hydrogen; (b) cycloalkyl; (c) alkenyl; (d) cycloalkenyl; (e) alkyl; (f) phenyl; (g) alkoxy; (h) alkoxy alkyl; and (i) alkoxycarbonylalkyl.
摘要翻译： 公开了作为环境指示材料有用的乙炔配合物，由此其暴露于环境刺激物引起颜色变化。 这些络合物含有至少一种有效的络合金属和至少一种具有以下通式的炔属化合物：[R-（C“C）a-（CH 2）b - （C”C）c] 2.dHX其中a为1或 2，b约为0-5; c为0或1; 条件是当a为1时，b和c为0，当a为2时，b为约0-5，c为0或1; 并且R是 - （CH 2）n -NHC（O）NHR'; 其中n为约1至10的整数; 和R'选自：（a）氢; （b）环烷基; （c）烯基; （d）环烯基; （e）烷基; （f）苯基; （g）烷氧基; （h）烷氧基烷基; 和（i）烷氧基羰基烷基。
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公开(公告)号：US4220747A
公开(公告)日：1980-09-02
申请号：US700626
申请日：1976-06-28
IPC分类号： C08F38/00
CPC分类号： C08F38/00
摘要： Liquid phase processable crystalline diacetylene polymers are obtained by the solid state reaction of monomers having the formulaR.sub.1 --C.tbd.C--C.tbd.C--R.sub.2where R.sub.1 and R.sub.2 are independently selected from the group consisting of(a) CH.sub.3 (CH.sub.2).sub.m --(b) HO(CH.sub.2).sub.n -- and(c) R.sub.3 NHOCO(CH.sub.2).sub.p --where "m" is an integer of from 0 to 15, "n" is an integer of from 1 to 15, "p" is an integer of from 1 to 15, and R.sub.3 is a member selected from the group consisting of(i) C.sub.6 H.sub.5 (CH.sub.2).sub.r --(ii) CH.sub.3 (CH.sub.2).sub.r -- and(iii) C.sub.10 H.sub.7 (CH.sub.2).sub.r --where "r" is an integer of from 0 to 11; with the proviso that where R.sub.1 and R.sub.2 are the same and are either (b) or (c), neither "n" nor "p" equals 1; and with the further proviso that where R.sub.1 and R.sub.2 are different and are either (b) or (c), the sum of "n" plus "p" is greater than 2.Polymerization proceeds by 1,4-addition reaction at each diacetylene group to produce a crystalline diacetylene polymer having the structure ##STR1## or the alternate head-to-head structure: where R.sub.1 and R.sub.2 are as defined above. The structure of such polymers is characterized by Raman intense .nu..sub.C.dbd.C and .nu.C.tbd.C vibrations at, respectively 1450 to 1540 cm.sup.-1 and 2060 to 2140 cm.sup.-1, which replace the Raman intense .nu..sub.C.tbd.C vibration at approximately 2260 cm.sup.-1 in the monomer. The polymers are further characterized by intense optical dichroism, which is indicative of a high degree of chain alignment, and by high thermal dimensional stability. They are useful as photoconductive materials, pigments, high strength materials, and optical polarizers.
摘要翻译： 液相可加工的结晶二乙炔聚合物通过具有式R1-C 3BOND CC 3BOND C-R2的单体的固态反应获得，其中R 1和R 2独立地选自（a）CH 3（CH 2）m - （b ）HO（CH 2）n - 和（c）R 3 NHCOO（CH 2）p - ，其中“m”为0至15的整数，“n”为1至15的整数，“p” 1至15，并且R 3是选自（i）C 6 H 5（CH 2）r - （ii）CH 3（CH 2）r - 和（iii）C 10 H 7（CH 2）r - 的其中的“ 从0到11; 条件是其中R1和R2相同且为（b）或（c），“n”和“p”均不为1; 并且进一步的条件是当R 1和R 2不同且为（b）或（c））时，“n”加“p”的总和大于2.聚合在每个二乙炔处进行1,4-加成反应 以产生具有结构“IMAGE”或替代头对头结构的结晶二乙炔聚合物：其中R 1和R 2如上所定义。 这种聚合物的结构的特征在于分别为1450至1540cm -1和2060至2140cm -1的拉曼强烈nu C = C和nu C 3BOND C振动，其在大约2260℃时代替拉曼强烈的nu C 3BOND C振动 cm-1。 聚合物的进一步特征在于强光学二色性，其表现出高度的链对齐性和高的热尺寸稳定性。 它们可用作感光材料，颜料，高强度材料和光学偏振器。
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公开(公告)号：US3999946A
公开(公告)日：1976-12-28
申请号：US660562
申请日：1976-02-23
CPC分类号： G01N31/229 , G01N33/02 , Y10S252/962
摘要： Compositions containing at least two conjugated acetylene groups (-C.tbd.C-C.tbd.C-) are suitable as integral time-temperature history indicators. These compositions exhibit sequences of irreversible color changes at combinations of times and temperatures specific to each composition. Thus, when supported on the surface of a product or on a substrate affixed to a product, they are useful for indicating whether a perishable (e.g., foodstuff, pharmaceutical, chemical, etc.) has been exposed to an undesirable time-temperature history that results in substantial degradation of the perishable or whether a product has been exposed to a desirable time-temperature history during processing (e.g., the sterilization of a foodstuff or biomedical material).
摘要翻译： 含有至少两个共轭乙炔基团（-C3ON C-C 3BOND-C）的组合物适合作为积分时间历史指标。 这些组合物在每种组合物特异性的时间和温度的组合中显示出不可逆的颜色变化的序列。 因此，当被支撑在产品的表面上或固定在产品上的基板上时，它们可用于指示易腐烂的（例如，食品，药物，化学品等）是否暴露于不期望的时间 - 温度历史， 导致易腐物质的显着降解，或者产品在加工过程中是否已经暴露于期望的时间 - 温度历史（例如，食品或生物医学材料的灭菌）。
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公开(公告)号：US4892677A
公开(公告)日：1990-01-09
申请号：US683443
申请日：1984-12-19
CPC分类号： G07C1/00 , G01N31/229 , Y10S252/962 , Y10S428/913
摘要： A new process is described which is useful for producing novel articles of manufacture useful for monitoring the time-temperature history of perishable items. The process initially involves forming a solution comprised of a diacetylenic monomer and a solvent. The solution is frozen, and the frozen solution having crystalline diacetylenic monomer therein is irradiated to partially polymerize the diacetylenic monomer. Partial polymerization of the crystalline diacetylenic monomer admixed with frozen solvent results in the production of a novel article of manufacture having color. The novel article of manufacture is comprised of frozen solvent, diacetylenic monomer, and colored polydiacetylene. Due to the intensity of the color of the polydiacetylene, the entire article of manufacture appears to be colored.The colored article of manufacture may be attached to various perishables to monitor the shelf life of the perishables. upon exposure to temperatures above a critical temperature, the frozen solvent melts and extracts unreached monomer from the colored polymer, thereby causing a sharp color transition which indicates that the perishable should possibly be discarded.
摘要翻译： 描述了一种新方法，其可用于生产可用于监测易腐物品的时间 - 温度历史的新型制品。 该方法最初涉及形成由二乙炔单体和溶剂组成的溶液。 将溶液冷冻，照射其中具有结晶二炔单体的冷冻溶液以部分聚合二乙炔单体。 与冷冻溶剂混合的结晶二乙炔单体的部分聚合导致生产具有颜色的新型制品。 新型制品由冷冻溶剂，二乙炔单体和着色聚二乙炔组成。 由于聚二乙炔颜色的强度，整个制品似乎是有色的。 有色制品可以附着在各种易腐食品上，以监测易腐品的保质期。 在暴露于高于临界温度的温度下，冷冻的溶剂熔融并从着色聚合物中提取未接触的单体，从而引起明显的颜色转变，这表明易腐物质可能被丢弃。
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6.发明授权Acid complexed acetylenic compounds useful as environmental indicating materials 失效酸性络合的炔属化合物可用作环境指示材料
公开(公告)号：US4789637A
公开(公告)日：1988-12-06
申请号：US912713
申请日：1986-09-29
IPC分类号： G01N31/22 , G01N33/02 , C07C127/15 , G01K11/14
摘要： A family of acetylenic complexes especially useful as environmental indicators is provided. The complexes include at least one complexing acid and one acetylenic compound of the formula:[R--(C.tbd.C).sub.a --(CH.sub.2).sub.b --(C.tbd.C).sub.c ].sub.2.dHXwherein, a is 1 or 2; b is about 0-5; c is 0 or 1; d is above 0 to about 2, with the proviso that when a is 1, b and c are 0, and when a is 2, b is about 0-5 and c is 0 or 1; and R is --(CH.sub.2)n--NHC(O)NHR'; wherein n is an integer of about 1 to 10; and R' is selected from a group consisting of hydrogen, cycloalkyl, alkenyl, cycloalkenyl, aklyl, phenyl, alkoxyl, alkoxylcarbonylalkyl, and X is a complexing acid.
摘要翻译： 提供了特别用作环境指标的炔属复合物系列。 络合物包括至少一种络合酸和一个下式的炔属化合物：[R-（C 3 B）C - （CH 2）b - （C 3 F 3）C] 2 dHX其中a为1或2; b约为0-5; c为0或1; d大于0至约2，条件是当a为1时，b和c为0，当a为2时，b为约0-5，c为0或1; 并且R是 - （CH 2）n -NHC（O）NHR'; 其中n为约1至10的整数; 并且R'选自氢，环烷基，烯基，环烯基，烷基，苯基，烷氧基，烷氧基羰基烷基，X是络合酸。
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公开(公告)号：US4699997A
公开(公告)日：1987-10-13
申请号：US425145
申请日：1982-09-28
IPC分类号： B01J39/20 , C07C29/44 , C07C29/62 , C07C33/04 , C07C33/044 , C07C57/24 , C08F38/00 , C22B3/26 , C22B3/44 , C07C125/073
CPC分类号： C07C57/24 , B01J39/20 , C07C29/44 , C07C29/62 , C07C33/04 , C07C33/044 , C08F38/00 , C22B3/0097 , C22B3/44 , Y02P10/234
摘要： Water-soluble polyacetylenic alkali metal salts from monomers and polymers of carboxymethyl urethanes of di-, tetra-, and hexayne diols, or from the corresponding diacids; useful in thermal and irradiation exposure indicators and/or in detection and/or removal of nonalkali metal ions dissolved in aqueous media.
摘要翻译： 来自单体的水溶性聚乙炔碱金属盐，二 - ，四 - 和六烯二醇的羧甲基氨基甲酸酯或相应的二酸的聚合物; 可用于热和照射暴露指示剂和/或在检测和/或去除溶解在水性介质中的非碱性金属离子。
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8.发明授权Metal salts of polyacetylenic compounds and uses thereof as ion exchange and thermochromic polymers 失效聚乙炔化合物的金属盐及其用作离子交换和热变色聚合物
公开(公告)号：US4373032A
公开(公告)日：1983-02-08
申请号：US159741
申请日：1980-06-16
IPC分类号： C07C57/18 , B01J39/20 , C07C29/44 , C07C29/62 , C07C33/04 , C07C33/044 , C07C51/00 , C07C57/24 , C07C67/00 , C07C239/00 , C07C271/22 , C08F38/00 , C22B3/26 , C22B3/44 , C08F38/02 , C08F2/46
CPC分类号： C08F38/00 , B01J39/20 , C07C29/44 , C07C29/62 , C07C33/04 , C07C33/044 , C07C57/24 , C22B3/0097 , C22B3/44 , Y02P10/234
摘要： Water-soluble polyacetylenic alkali metal salts from monomers and polymers of carboxymethyl urethanes of di-, tetra-, and hexayne diols, or from the corresponding diacids; useful in thermal and irradiation exposure indicators and/or in detection and/or removal of nonalkali metal ions dissolved in aqueous media.
摘要翻译： 来自单体的水溶性聚乙炔碱金属盐，二 - ，四 - 和六烯二醇的羧甲基氨基甲酸酯或相应的二酸的聚合物; 可用于热和照射暴露指示剂和/或在检测和/或去除溶解在水性介质中的非碱性金属离子。
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9.发明授权
公开(公告)号：US4255535A
公开(公告)日：1981-03-10
申请号：US970093
申请日：1978-12-15
摘要： There are provided composites having near-zero uniaxial thermal expansion coefficients. One or more polyacetylenes having a negative uniaxial thermal expansion coefficient are uniaxially or biaxially oriented within one or more solid matrix materials having a positive thermal expansion coefficient to yield a composite material having a uniaxial thermal expansion coefficient which is nearly zero. The polyacetylenes are obtained by the solid-state polymerization of crystals of monomers containing at least one --C.tbd.C--C.tbd.C-- grouping per molecule. Also provided are processes for producing the above-described composites.
摘要翻译： 提供具有近零单轴热膨胀系数的复合材料。 具有负单轴热膨胀系数的一种或多种聚乙炔在具有正热膨胀系数的一种或多种固体基质材料中单轴或双轴取向，得到具有几乎为零的单轴热膨胀系数的复合材料。 聚乙炔通过每分子含有至少一个-C 3 C 1 -C 3 C 3 C C基团的单体的晶体的固态聚合而获得。 还提供了用于生产上述复合材料的方法。
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公开(公告)号：US4735745A
公开(公告)日：1988-04-05
申请号：US373955
申请日：1982-05-03
CPC分类号： G07C1/00 , G01N31/229 , Y10S252/962 , Y10S428/913
摘要： A new process is described which is useful for producing novel articles of manufacture useful for monitoring the time-temperature history of perishable items. The process initially involves forming a solution comprised of a diacetylenic monomer and a solvent. The solution is frozen, and the frozen solution having crystalline diacetylenic monomer therein is irradiated to partially polymerize the diacetylenic monomer. Partial polymerization of the crystalline diacetylenic monomer admixed with frozen solvent results in the production of a novel article of manufacture having color. The novel article of manufacture is comprised of frozen solvent, diacetylenic monomer, and colored polydiacetylene. Due to the intensity of the color of the polydiacetylene, the entire article of manufacture appears to be colored.The colored article of manufacture may be attached to various perishables to monitor the shelf life of the perishables. Upon exposure to temperatures above a critical temperature, the frozen solvent melts and extracts unreacted monomer from the colored polymer, thereby causing a sharp color transition which indicates that the perishable should possibly be discarded.
摘要翻译： 描述了一种新方法，其可用于生产可用于监测易腐物品的时间 - 温度历史的新型制品。 该方法最初涉及形成由二乙炔单体和溶剂组成的溶液。 将溶液冷冻，照射其中具有结晶二炔单体的冷冻溶液以部分聚合二乙炔单体。 与冷冻溶剂混合的结晶二乙炔单体的部分聚合导致生产具有颜色的新型制品。 新型制品由冷冻溶剂，二乙炔单体和着色聚二乙炔组成。 由于聚二乙炔颜色的强度，整个制品似乎是有色的。 有色制品可以附着在各种易腐食品上，以监测易腐品的保质期。 当暴露于高于临界温度的温度时，冷冻溶剂从着色聚合物中熔融并提取未反应的单体，从而引起明显的颜色转变，这表明易腐烂物可能被丢弃。
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