Terminally unsaturated macromolecular monomers of polylactones and
copolymers thereof
    2.
    发明授权
    Terminally unsaturated macromolecular monomers of polylactones and copolymers thereof 失效
    聚内酯的末端不饱和高分子单体及其共聚物

    公开(公告)号:US4791189A

    公开(公告)日:1988-12-13

    申请号:US46818

    申请日:1987-05-07

    申请人: Simon H. Yu

    发明人: Simon H. Yu

    CPC分类号: C08G63/08 C08G63/664

    摘要: Preparation of a macromolecular monomer of a lactone allows the preparation of copolymers of lactones with commonly available olefinically unsaturated monomers. There is no known method for the preparation of such copolymers. A cationic ring-opening polymerization of a lactone in conjunction with an unsaturated alcohol (propagator) having an acryloyl, allyl or styryl double bond, produces a polylactone macromer having an ethylenic double bond at one end and a hydroxyl group at the other. The polymerization proceeds by polyaddition of the lactone to the OH group which is the propagating species. The polylactone may include a polymeric or non-polymeric spacer. The propagator is a primary or secondary alcohol which, if cyclic may have a single internal double bond in one ring. The catalyst is an oxonium salt, or etherate of boron trifluoride. The macromer may be copolymerized with a wide variety of olefinically unsaturated monomers to form a macromer copolymer with pendant polylactone chains. In particular, block copolymers of terminally unsaturated macromers of ether-ester, or ester-ether structure may be tailored for specific applications.

    Process for making comb-shaped copolymers of a macromolecular monomer of
polylactone with terminal acryloyl unsaturation, and compatible blends
thereof
    3.
    发明授权
    Process for making comb-shaped copolymers of a macromolecular monomer of polylactone with terminal acryloyl unsaturation, and compatible blends thereof 失效
    用于制备聚内酯的高分子单体与末端丙烯酰基不饱和键的梳状共聚物的方法及其相容的共混物

    公开(公告)号:US5061772A

    公开(公告)日:1991-10-29

    申请号:US638275

    申请日:1991-01-07

    申请人: Simon H. Yu

    发明人: Simon H. Yu

    IPC分类号: C08G63/08 C08G63/664

    CPC分类号: C08G63/664 C08G63/08

    摘要: A comb-shaped polymer ("comb" for brevity) of a polymerizable olefinically unsaturated monomer, preferably a vinyl, styryl, or acryloyl monomer, and a macromolecular monomer of a polylactone having an acryloyl or metharcryloyl "head" is effected at low temperature in an emulsion or suspension polymerization process. The processes are capable of producing a comb with a hydrocarbon backbone and pendant polyactone chains, which comb has a number average molecular weight of at least 10,000 without the use of a co-solvent. A comb with such high mol wt is not produced with a conventional solution polymerization process. A compatible blend is produced of a comb having a backbone incompatible with a synthetic resin, on the condition the polyactone chains are long enough to be compatible in the resin. A compatible blend of first and second resins, irrespective of whether they are compatible with each other, is also produced using a comb in which the backbone is compatible with one of the resins. Such blends also result with a synthetic resin and a comb in which the pendant chains consist of a first block which has a polylactone structure, and a second block which has a polyether structure, or vice versa.

    摘要翻译: 可聚合的烯属不饱和单体,优选乙烯基,苯乙烯基或丙烯酰基单体的梳状聚合物(简称为“梳子”)和具有丙烯酰基或甲基丙烯酰基“头”的聚内酯的高分子单体在低温下进行 乳液或悬浮聚合方法。 该方法能够产生具有烃骨架和侧链聚内酯链的梳子,该梳子的数均分子量至少为10,000,而不使用共溶剂。 用常规的溶液聚合方法不会产生具有这样高的摩尔重量的梳子。 在具有与合成树脂不相容的骨架的梳子上制备相容的共混物,在该聚合物链长到足以在树脂中相容的条件下。 第一和第二树脂的相容混合物,不管它们是否彼此相容,也是使用其中骨架与其中一种树脂相容的梳制成的。 这种共混物还产生合成树脂和梳子,其中侧链由具有聚内酯结构的第一嵌段和具有聚醚结构的第二嵌段组成,反之亦然。

    Terminally unsaturated macromolecular monomers of polyformals and
copolymers thereof
    4.
    发明授权
    Terminally unsaturated macromolecular monomers of polyformals and copolymers thereof 失效
    聚异戊二烯的端不饱和高分子单体及其共聚物

    公开(公告)号:US4847332A

    公开(公告)日:1989-07-11

    申请号:US129613

    申请日:1987-12-07

    申请人: Simon H. Yu

    发明人: Simon H. Yu

    CPC分类号: C08G2/30 C08F290/062

    摘要: Cyclic formals, other than trioxane, form macromers with an olefinically unsaturated alcohol which functions as a propagating species to form a macromer of polyformal having a molecular weight generally less than about 10,000. A cationically ring-openable ether may be used to provide a polyether spacer in the alkenyl alcohol so that the macromer of polyformal formed contains a polyether block. Thus, the polyformal macromer may have a acryloyl, allyl, or styryl head group. Macromers of polyformal block copolymers are formed sequentially by first forming the block of first formal and then without isolating the macromer so formed, sequentially polymerizing a second formal monomer to form the second formal block. A macromer of randon copolymer may be formed with one or more cyclic formals or a cyclic ether. Macromers of random copolymers may also be formed with formaldehyde or trioxane. After a macromer of polyformal is formed, it may be isolated and used as a propagating species to provide a block copolymer with a polyether or with another formal. A macromer of polyformal may also be used to copolymerize an olefinic monomer to yield comb or graft copolymers in whcih the macromer chains are pendant. An end-capped macromer of polyformal may be used to form nonhydrolyzable formal-siloxane block copolymers.

    摘要翻译: 与三恶烷以外的环形成型体形成具有烯属不饱和醇的大分子单体,其作为增殖物质起作用以形成分子量通常小于约10,000的聚甲醛的大分子单体。 可以使用阳离子可开环醚在烯基醇中提供聚醚间隔基,使得形成的聚甲醛的大分子单体包含聚醚嵌段。 因此,聚甲醛大分子单体可以具有丙烯酰基,烯丙基或苯乙烯基头基。 多形式嵌段共聚物的大单体通过首先形成第一种形式的嵌段,然后不分离如此形成的大分子单体顺序形成,依次聚合第二种形式单体以形成第二形式嵌段。 兰顿共聚物的大分子单体可以与一种或多种环状形式或环状醚形成。 无规共聚物的大单体也可以用甲醛或三恶烷形成。 在形成聚甲醛的大分子单体之后,可以将其分离并用作传播物质以提供与聚醚或其它形式的嵌段共聚物。 多聚甲醛的大分子单体也可以用于共聚烯烃单体以产生梳子或接枝共聚物,大分子单体链是悬挂的。 可以使用聚甲醛封端的大分子单体形成不可水解的形式 - 硅氧烷嵌段共聚物。

    Reactive modifier of elastomeric comb copolymer for thermosetting resins
and process for making the same
    5.
    发明授权
    Reactive modifier of elastomeric comb copolymer for thermosetting resins and process for making the same 失效
    用于热固性树脂的弹性梳状共聚物的反应性改性剂及其制备方法

    公开(公告)号:US5506320A

    公开(公告)日:1996-04-09

    申请号:US87546

    申请日:1993-07-06

    申请人: Simon H. Yu

    发明人: Simon H. Yu

    摘要: A reactive polymeric modifier to improve toughness and/or flexibility of thermosetting resins where the polymer has a comb configuration including a saturated polymeric backbone having reactive groups at each end and at least one pendent chain which is miscible with the thermosetting resin while it is uncured; the backbone being a polymeric chain of carbon-carbon linkages free of olefinic unsaturation, having a glass transition temperature Tg in the range from -100.degree. C. to 25.degree. C.;the reactive groups being reactive with the thermosetting resin, being positioned on both ends of the backbone, and comprising, on average, at least 1.2 but less than 2 reactive groups positioned so as to yield a substantially difunctionalized comb;the pendent chain or chains being linked to said backbone, being present in an amount in the range from 3% to 40% by weight of said comb copolymer, and having from 2 to 250 repeating units selected from the group consisting of polyester, polyether, polystyrene, and polymethacrylate; and,the comb polymer having a number average molecular weight in the range from 1,000 to 20,000, and a process for making the modifier.

    摘要翻译: 一种反应性聚合物改性剂,用于改善热固性树脂的韧性和/或柔性,其中聚合物具有包括在每个端部具有反应性基团的饱和聚合物主链的梳形结构和至少一种在未固化时可与热固性树脂混溶的侧链; 骨架是不含烯属不饱和键的碳 - 碳键的聚合物链,其玻璃化转变温度Tg在-100℃至25℃的范围内。 反应性基团与热固性树脂反应,位于主链的两端,平均包含至少1.2个但小于2个反应性基团,其定位为产生基本上双官能化的梳子; 连接到所述主链的侧链或链以所述梳状共聚物的3重量%至40重量%的量存在,并且具有2至250个选自聚酯,聚醚, 聚苯乙烯和聚甲基丙烯酸酯; 并且数均分子量在1,000〜20,000的梳型聚合物和制造改性剂的方法。

    Blends of comb-shaped copolymers of a macromolecular monomer of
polyhaloether with terminal olefinic unsaturation
    6.
    发明授权
    Blends of comb-shaped copolymers of a macromolecular monomer of polyhaloether with terminal olefinic unsaturation 失效
    聚乙二醇的分子单体与终端烯烃不稳定的共形共聚物的共混

    公开(公告)号:US5177151A

    公开(公告)日:1993-01-05

    申请号:US895504

    申请日:1992-06-08

    申请人: Simon H. Yu

    发明人: Simon H. Yu

    IPC分类号: C08G63/08 C08G63/664

    CPC分类号: C08G63/664 C08G63/08

    摘要: This invention relates to a comb-shaped graft copolymer, to a process for making the comb, and to a polymer blend made with the comb. The comb is made by a free radical polymerization of an ethylenically unsaturated monomer with a macromolecular monomer ("macromer" for brevity) of a haloalkylene oxide ("HAO" for brevity) homopolymer, random or block copolymer. The comb copolymer and blends of the comb with a polymer(s) may be cured. A comb with a terminal acrylyl or methacrylyl group or "head" and pendant polyether chains, which always include some HAO repeating units, may be made in an emulsion or suspension polymerization process which provides a comb having adequately high molecular weight so that the comb may be used in blends. The preferred comb of epichlorohydrin has a (meth)acrylyl head at one end, through which it (the macromer) is polymerizable, and a terminal hydroxyl (OH) group, or an end-capping group derived from the OH group at the other end. Each "tine" (pendant chain) of the comb is an uninterrupted one (that is, having no branch) having at least two repeating units derived from a HAO, preferably epichlorohydrin ("ECH"), with the tine terminating with a OH group, or an end-capping group derived from the OH group.

    摘要翻译: 本发明涉及梳状接枝共聚物,制造梳子的方法,以及由梳子制成的聚合物共混物。 通过烯键式不饱和单体与大分子单体(简称为“大分子单体”)的卤代环氧烷(简称“HAO”)均聚物,无规或嵌段共聚物的自由基聚合制成梳子。 梳状共聚物和梳子与聚合物的共混物可以固化。 总是包含一些HAO重复单元的末端丙烯酰基或甲基丙烯酰基或“头”和侧挂聚醚链的梳子可以在乳液或悬浮聚合方法中制备,其提供具有足够高分子量的梳子,使得梳子可以 用于混合物。 表氯醇的优选梳在一端具有(甲基)丙烯酰头,其(大分子单体)可以通过其聚合,并且末端羟基(OH)基团或衍生自另一端的OH基团的封端基 。 梳子的每个“齿”(侧链)是具有至少两个衍生自HAO的重复单元(优选表氯醇(“ECH”))的不间断的(即没有分支),其中终止于OH基团 或衍生自OH基团的封端基团。

    Blends of comb-shaped copolymers of a macromolecular monomer of
polylactone with polymer (s)
    7.
    发明授权
    Blends of comb-shaped copolymers of a macromolecular monomer of polylactone with polymer (s) 失效
    聚内酯的大分子单体与聚合物的梳状共聚物的共混物

    公开(公告)号:US5120790A

    公开(公告)日:1992-06-09

    申请号:US783944

    申请日:1991-10-28

    申请人: Simon H. Yu

    发明人: Simon H. Yu

    摘要: Blends are formed with numerous commercially available resins and a comb-shaped polymer ("comb" for brevity) of a macromolecular monomer of a polylactone having terminal vinyl unsaturation so long as the polylactone chains are long enough to be compatible with one of the components to be blended. The comb may be formed with any polymerizable olefinically unsaturated monomer, preferably a vinyl, styryl, or acryloyl monomer. The vinyl unsaturation of the "head" of the macromer of polylactone may be acryloyl, styryl or allyl. The comb is made by a low temperature emulsion or suspension polymerization process. The comb, which has a hydrocarbon backbone and pendant polylactone chains, typically has a number average molecular weight of at least 10,000. A blend of first and second resins which are normally incompatible with each other, is also produced using a comb in which the backbone is compatible with one of the resins. Such blends also result with a synthetic resin and a comb in which the pendant chains consist of a first block which has a polylactone structure, and a second block which has a polyether structure, or vice versa.

    摘要翻译: 混合物由许多可商购的树脂和具有末端乙烯基不饱和键的聚内酯的大分子单体的梳状聚合物(“梳子”)形成,只要聚内酯链足够长以与其中一种组分相容即可 混合 梳子可以用任何可聚合的烯属不饱和单体形成,优选乙烯基,苯乙烯基或丙烯酰基单体。 聚内酯大分子单体的“头”的乙烯基不饱和度可以是丙烯酰基,苯乙烯基或烯丙基。 梳子由低温乳液或悬浮聚合法制成。 具有烃骨架和侧链聚内酯链的梳子通常具有至少10,000的数均分子量。 通常彼此不相容的第一和第二树脂的共混物也使用其中骨架与树脂之一相容的梳子生产。 这种共混物还产生合成树脂和梳子,其中侧链由具有聚内酯结构的第一嵌段和具有聚醚结构的第二嵌段组成,反之亦然。

    Allyl terminated macromolecular monomers of polyethers
    8.
    发明授权
    Allyl terminated macromolecular monomers of polyethers 失效
    聚醚的烯丙基封端的大分子单体

    公开(公告)号:US4722978A

    公开(公告)日:1988-02-02

    申请号:US771093

    申请日:1985-08-30

    申请人: Simon H. Yu

    发明人: Simon H. Yu

    摘要: A cationic ring-opening polymerization of a cyclic ether ("CE") in conjunction with an unsaturated alcohol (propagator) having an allyl double bond, produces a polyether macromer having an allylic group near one end and a hydroxyl group at the other. The polymerization proceeds by polyaddition of the CE to the OH group which is the propagating species. The CE is an alkylene oxide or an aliphatic or aromatic glycidyl ether; the propagator is a primary or secondary alcohol which, if cyclic may have a single internal double bond in one ring. The catalyst is a Friedel-Crafts acid, strong protic organic or inorganic acid, oxonium salt, or the like. The macromer formed may be homopolymerized to yield a polyvinyl homomacromer with pendant chains of polymerized CE; or the CE may be copolymerized with a wide variety of olefinically unsaturated monomers to form a macromer copolymer; or, plural cyclic ethers may be (a) sequentially polymerized to form macromer block copolyethers, or, (b) polymerized randomly to form macromer copolyether copolymers. The cationically ring-opened macromer formed always contains a trace of a cyclic oligomer of the CE.

    摘要翻译: 环状醚(“CE”)与具有烯丙基双键的不饱和醇(传播剂)的阳离子开环聚合产生在一端具有烯丙基并在另一端具有羟基的聚醚大分子单体。 通过将CE加成到作为增殖物质的OH基团进行聚合。 CE是环氧烷或脂族或芳族缩水甘油醚; 传播者是伯或仲醇,如果在一个环中循环可以具有单个内部双键。 该催化剂是Friedel-Crafts酸,强质子有机或无机酸,氧鎓盐等。 形成的大分子单体可以均聚,得到具有聚合的CE的侧链的聚乙烯基同质异构体; 或者CE可以与各种烯属不饱和单体共聚以形成大分子单体共聚物; 或多个环醚可以(a)顺序聚合以形成大分子嵌段共聚醚,或(b)随机聚合以形成大分子单体共聚醚共聚物。 所形成的阳离子开环大分子单体总是含有CE的环状低聚物的痕迹。

    Comb-shaped copolymers of a macromolecular monomer of polyhaloether with
terminal olefinic unsaturation and process
    10.
    发明授权
    Comb-shaped copolymers of a macromolecular monomer of polyhaloether with terminal olefinic unsaturation and process 失效
    聚卤醚的大分子单体与末端烯属不饱和键的过程的梳状共聚物

    公开(公告)号:US5225491A

    公开(公告)日:1993-07-06

    申请号:US960673

    申请日:1992-10-14

    申请人: Simon H. Yu

    发明人: Simon H. Yu

    摘要: This invention relates to a comb-shaped graft copolymer, to a process for making the comb, and to a polymer blend made with the comb. The comb is made by a free radical polymerization of an ethylenically unsaturated monomer with a macromolecular monomer ("macromer" for brevity) of a haloalkylene oxide ("HAO" for brevity) homopolymer, random or block copolymer. The comb copolymer and blends of the comb with a polymer(s) may be cured. A comb with a terminal acrylyl or methacrylyl group or "head" and pendant polyether chains, which always include some HAO repeating units, may be made in an emulsion or suspension polymerization process which provides a comb having adequately high molecular weight so that the comb may be used in blends. The preferred comb of epichlorohydrin has a (meth)acrylyl head at one end, through which it (the macromer) is polymerizable, and a terminal hydroxyl (OH) group, or an end-capping group derived from the OH group at the other end. Each "tine" (pendant chain) of the comb is an uninterrupted one (that is, having no branch) having at least two repeating units derived from a HAO, preferably epichlorohydrin ("ECH"), with the tine terminating with a OH group, or an end-capping group derived from the OH group.

    摘要翻译: 本发明涉及梳状接枝共聚物,制造梳子的方法,以及由梳子制成的聚合物共混物。 通过烯键式不饱和单体与大分子单体(简称为“大分子单体”)的卤代环氧烷(简称“HAO”)均聚物,无规或嵌段共聚物的自由基聚合制成梳子。 梳状共聚物和梳子与聚合物的共混物可以固化。 总是包含一些HAO重复单元的末端丙烯酰基或甲基丙烯酰基或“头”和侧挂聚醚链的梳子可以在乳液或悬浮聚合方法中制备,其提供具有足够高分子量的梳子,使得梳子可以 用于混合物。 表氯醇的优选梳在一端具有(甲基)丙烯酰头,其(大分子单体)可以通过其聚合,并且末端羟基(OH)基团或衍生自另一端的OH基团的封端基 。 梳子的每个“齿”(侧链)是具有至少两个衍生自HAO的重复单元(优选表氯醇(“ECH”))的不间断的(即没有分支),其中终止于OH基团 或衍生自OH基团的封端基团。