<2-Methylamino-ethyl>-vinyl-sulfid | 108723-44-0

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: <2-Methylamino-ethyl>-vinyl-sulfid
• 英文别名: <2-Methylamino-ethyl>-vinylsulfid；(2-Methylamino-ethyl)-vinyl-sulfid；2-ethenylsulfanyl-N-methylethanamine
• CAS: 108723-44-0
• 化学式: C₅H₁₁NS
• mdl: MFCD19218488
• 分子量: 117.215
• InChiKey: OHWBJBZVYGDDNO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.9
• 重原子数：
  7
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  37.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  potassium cyanate 、 <2-Methylamino-ethyl>-vinyl-sulfid 在 盐酸 、 甲醇 作用下， 生成 N-methyl-N-(2-vinylmercapto-ethyl)-urea
  参考文献：
  名称：

  Vinyl sulfides of substituted ureas and thioureas, polymers thereof, and methods for making them

  摘要：

  本发明涉及以下化合物的聚合物和共聚物：-I：CH2 = CH，S，#j（NHCX）nNR1R2；II：CH2 = CH，S，A，NR3，CX，NR1R2；III：（CH2 = CH.S.#j.NH.CX.NH）mR4；IV：（CH2 = CH.S.A.NR3.CX.NH）mR4，其中A是C2-C6烷基，#j是o-或p-苯基，可选择单或双取代C1-C4烷基，R1是H，C1-C18烷基，烯基，环烷基，芳基或氯芳基，R2是H，甲基或乙基（或NR1R2是吗啡啉，哌啶或吡咯啉残基），R3是H或C1-C4烷基，R4是C4-C10烷基，苯基，甲苯基，亚甲基-双苯基，甲基亚苯基或二苯基甲烷，X是O或S，m为2或3，n为1，或者如果R1 = R2 = H且X = O，则为2。可以使用有机过氧化物，偶氮化合物，三氟化硼，二氧化硫，三氯化锡或氯化铝作为催化剂，在块状，溶液，乳液或悬浮液中进行聚合。这些化合物可以与丙烯酸和甲基丙烯酸，酯，酰胺和腈共聚；马来酸，富马酸，异柠檬酸和柠檬酸酯的酯；乙烯和乙烯基氧基烷基羧酸酯；乙烯基烷基和羟基烷基醚；乙烯和乙烯基卤化物；乙酰基丁二烯；乙烯，苯乙烯和二乙烯基苯；乙二酸乙烯酯和二甲基丙烯酸酯；乙烯氧基丙烯酸酯；双（乙烯氧基乙基）脲。含有-NH，CX，NH-基团的单体或聚合物通过与甲醛处理形成甲醇衍生物，这些甲醇衍生物可以酸缩成亚甲基双化合物。无法熔融的产品也可通过进一步加热无甲醇聚合物获得。单体中的硫化物基团可以氧化为硫氧化物或磺酸基团，在这种情况下，聚合是用阴离子或碱性催化剂进行的，例如氢化钠，氢化钾或锂烷基。示例显示了N-乙基-N1-甲基-N1-2-（乙烯硫基）-乙基脲，N1-甲基-N1-2-（乙烯硫基）-乙基吗啡啉-N-羧酰胺和N-十八烷基-N1-2-（乙烯硫基）-丙基脲的聚合，以及以下共聚物的制备：（1）N-乙基-N1-甲基-N1-2-（乙烯硫基）-乙基脲或N1-甲基-N1-2-（乙烯硫基）-乙基吗啡啉-N-羧酰胺与甲基丙烯酸甲酯或丙烯腈共聚，后者可产生可纺织的纤维；以及（2）N-十八烷基-N1-甲基-N1-2-（乙烯硫基）-乙基硫脲与丁基丙烯酸酯。还说明了已六亚甲基双（N1-甲基-N1-2-（乙烯硫基）-乙基脲）与甲酰乙基乙烯醚，尿素乙烯醚，乙烯-脲基乙烯醚，丙烯酸烯丙酯，苯乙烯，乙酸乙烯酯，丙烯腈，丙烯酸酯和甲基丙烯酸酯共聚的聚合物。这些聚合物和共聚物（包括甲醇化衍生物）是纤维素醋酸或纤维素醋酸丁酸纺丝液的有用添加剂，其中N-乙基-N1-甲基-N1-2-（乙烯硫基）-乙基脲的聚合物被提及用于此目的。此外，本发明还涉及以下化合物：I：CH2 = CH.S.#j（NHCX）nNR1R2；II：CH2 = CH.S.A.NR3.CX.NR1R2；III：（CH2 = CH.S.#j.NH.CX.NH）mR4；IV：（CH2 = CH.S.A.NR3.CX.NH）mR4，其中A是C2-C6烷基，#j是o-或p-苯基，可选择单或双取代C1-C4烷基，R1是H，C1-C18烷基，烯基，环烷基，芳基或氯芳基，R2是H，甲基或乙基（或NR1R2是吗啡啉，哌啶或吡咯啉残基），R3是H或C1-C4烷基，R4是C4-C10烷基，苯基，甲苯基，亚甲基-双苯基，甲基亚苯基或二苯基甲烷，X是O或S，m为2或3，n为1，或者如果R1 = R2 = H且X = O，则为2。化合物I，其中n为2且X为O，是通过用碱金属氰酸盐和矿物酸处理胺CH2 = CH.S.#j.NH2制备的。化合物I和II，其中R1但不是R2为H，是从相应的胺和R2NCO或R2NCS制备的。化合物I和II，其中R1和R2都不是H，是从胺和R1R2 NCX.卤素制备的。化合物II，其中R1和R2都是H，是通过用矿物酸处理的氰酸盐或硫氰酸盐和胺融合而成的，这种方法也用于化合物I，其中n为I，X为S，R1和R2都是H。化合物III和IV是从胺和适当的二或三异氰酸酯或-异硫氰酸酯制备的。这些产品中的硫化物基团可以氧化为相应的硫氧化物和磺酸基团，并且可以添加巯基在b-位置上形成二硫化物。其中具有-NH.CX.NH-基团的化合物还与醛反应，特别是与甲醛反应形成甲醇衍生物，这些甲醇衍生物可以进一步缩合成亚甲基双化合物。示例显示了以下的制备：（1）从2-氨基乙基乙烯硫醚与氰酸钾和酸或与尿素加热制备2-尿素基乙基乙烯硫醚；（2）通过氰酸盐法制备（1）的N-甲基衍生物；（3）从2-（N-甲基氨基）-乙基乙烯硫醚分别与乙酰基异氰酸酯和十八烷基异氰酸酯反应制备N：N1-二取代脲；（4）从2-氨基苯基乙烯硫醚与氰酸钾和酸制备2-（乙烯硫基）-苯基双脲；（5）从2-氨基苯基乙烯硫醚和乙酰基异氰酸酯制备双取代脲；（6）从3-氨基丙基乙烯硫醚和二甲基氨基甲酰氯制备双取代脲；（7）从2-（N-甲基氨基）-乙基乙烯硫醚和吗啡啉-N-羧酸氯制备酰胺；（7）从2-氨基乙基乙烯硫醚和苯基异硫氰酸酯制备双取代硫脲；（8）从2-（N-甲基氨基）-乙基乙烯硫醚和t-辛基异硫氰酸酯制备双取代硫脲；（a）从2-（N-甲基氨基）-乙硫醚和己二酸二异氰酸酯和二苯甲烷-4：41-二异氰酸酯分别制备双脲；（10）通过加热2-氨基乙基乙烯硫醚和硫脲制备2-硫脲基乙基乙烯硫醚。还提到了其他适合的起始材料，其中A也可以是丙烯或异丁烯，#j可以是p-苯基，甲苯基或二甲苯基，R1可以是丙基，异丙基，丁基，异丁基，叔丁基，戊基，异戊基，己基，癸基，十二烷基，十六烷基，油酸基，环己基，氯苯基，萘基或苄基，R2可以是乙基，R3可以是丁基，R4可以是四亚甲基，十碳烷基，甲苯基，二甲苯基和亚甲基三苯基。N：N1-双（2-乙烯硫基乙基）-脲是通过加热2-氨基乙基乙烯硫醚和尿素制备的。未在N-原子上取代的氨基烷基和氨基芳基乙烯硫醚可由相应的巯基和乙炔与碱性催化剂反应制备。通过将硫脲与烷基氨基烷卤化物反应并用乙炔处理产生的异硫脲氢盐制备烷基氨基烷基乙烯硫醚。参见规范747,184。此外，本发明还涉及以下化合物：CH2 = CH，S，#j（NHCX）nNR1R2；CH2 = CH，S，A，NR3，CX，NR1R2；（CH2 = CH.S.#j.NH.CX.NH）mR4；（CH2 = CH.S.A.NR3.CX.NH）mR4，其中A是C2-C6烷基，#j是o-或p-苯基，可选择单或双取代C1-C4烷基，R1是H，C1-C18烷基，烯基，环烷基，芳基或氯芳基，R2是H，甲基或乙基（或NR1R2是吗啡啉，哌啶或吡咯啉残基），R3是H或C1-C4烷基，R4是C4-C10烷基，苯基，甲苯基，亚甲基-双苯基，甲基亚苯基或二苯基甲烷，X是O或S，m为2或3，n为1，或者如果R1 = R2 = H且X = O，则为2。将其中一种化合物从水或酒精溶液中施加到羊毛上，以与羊毛的SH基团反应；然后用甲醛和酸催化剂加热，从而改变手感和硬度，并减少收缩。此外，可以将其中一种化合物N-甲基化并应用于纺织品（特别是纤维素或玻璃纤维），以提供用于后续试剂的锚定位点。这些化合物的聚合物和共聚物还可在羊毛和纤维素织物上减少收缩。这些化合物的四种类型是CH2 = CH，S，#j（NHCXn）NR1R2，CH2 = CH，S，A，NR3，CX，NR1R2，（CH2 = CH，S，#j，NH，CX，NH）mR4和（CH2 = CH，S，A，NR3，CX，NH）mR4，其中A是C2-C6烷基，#j是o-或p-苯基，可选择单或双取代C1-C4烷基，R1是H，C1-C18烷基，烯基，环烷基，芳基或氯芳基，R2是H，甲基或乙基（或NR1R2是吗啡啉，哌啶或吡咯啉残基），R3是H或C1-C4烷基，R4是C4-C10烷基，苯基，甲苯基，亚甲基-双苯基，甲基亚苯基或二苯基甲烷，X是O或S，m为2或3，n为1，或者如果R1 = R2 = H且X = O，则为2。特别提到N-十八烷基-N1-2-（乙烯硫基）-丙基脲的聚合物赋予织物柔软的手感。此外，本发明还涉及以下化合物的聚合物和共聚物：CH2 = CH，S，#f（NHCXn）NR1R2，CH2 = CH，S，A，NR3，CX，NR1R2，（CH2 = CH，S，#f，NH，CX，NH）mR4和（CH2 = CH，S，A，NR3，CX，NH）mR4，其中A是C2-C6烷基，#f是o-或p-苯基，可选择单或双取代C1-C4烷基，R1是H，C1-C18烷基，烯基，环烷基，芳基或氯芳基，R2是H，甲基或乙基（或NR1R2是吗啡啉，哌啶或吡咯啉残基），R3是H或C1-C4烷基，R4是C4-C10烷基，苯基，甲苯基，亚甲基-双苯基，甲基亚苯基或二苯基甲烷，X是O或S，m为2或3，n为1，或者如果R1 = R2 = H且X = O，则为2。在一个例子中，用甲基丙烯酸甲酯和N-乙基-N1-甲基-N1-2-（乙烯硫基）-乙基脲的共聚物的乙氧基乙酸酯溶液加入二氧化钛处理金属板，然后烘烤；还可以存在尿素甲醛-丁醇缩合物和酸，例如丁酸邻苯二甲酸酯；板还可以是玻璃或陶瓷。N1-甲基-N1-2-（乙烯硫基）-乙基吗啡啉-N-羧酰胺的聚合物也被认为是一种有用的涂料材料。此外，本发明还涉及以下化合物：CH2 = CH，S，#f（NHCXn）NR1R2，CH2 = CH，S，A，NR3，CX，NR1R2，（CH2 = CH，S，#f，NH，CX，NH）mR4和（CH2 = CH，S，A，NR3，CX，NH）mR4，其中A是C2-C6烷基，#f是o-或p-苯基，可选择单或双取代C1-C4烷基，R1是H，C1-C18烷基，烯基，环烷基，芳基或氯芳基，R2是H，甲基或乙基（或NR1R2是吗啡啉，哌啶或吡咯啉残基），R3是H或C1-C4烷基，R4是C4

  公开号：

  US02858297A1
• 作为产物：
  描述：

  S-<2-Methylamino-ethyl>-isothiuroniumchlorid 、 乙炔 在 sodium hydroxide 作用下， 以 乙二醇二甲醚 为溶剂， 生成 <2-Methylamino-ethyl>-vinyl-sulfid
  参考文献：
  名称：

  Vinyl Sulfides. II. Aminoalkyl Vinyl Sulfides

  摘要：

  DOI：

  10.1021/jo01065a072

文献信息

• Vinyl Sulfides. II. Aminoalkyl Vinyl Sulfides
  作者：H. J. SCHNEIDER、J. J. BAGNELL、G. C. MURDOCH

  DOI：10.1021/jo01065a072

  日期：1961.6
• Vinyl sulfides of substituted ureas and thioureas, polymers thereof, and methods for making them
  申请人：ROHM & HAAS

  公开号：US02858297A1

  公开（公告）日：1958-10-28

  The invention comprises polymers and copolymers of compounds of the following formulae:-I: CH2=CH,S,#j(NHCX)nNR1R2; II: CH2=CH,S,A,NR3,CX,NR1R2; III:(CH2=CH.S.#j.NH.CX.NH)mR4; IV: (CH2=CH,S,A,NR3,CX,NH)mR4, where A is C2-C6 alkylene, #j is o- or p-phenylene optionally mono- or disubstituted by C1-C4 alkyl, R1 is H, C1-C18 alkyl, alkenyl, cycloalkyl, aralkyl, aryl or chloroaryl, R2 is H, methyl or ethyl (or NR1R2 is a morpholino, piperidino or pyrrolidino residue), R3 is H or C1-C4 alkyl, R4 is C4-C10 alkylene, phenylene, tolylene, methylene-bis-phenylene, methylidyne-tris-phenylene or dias nisylene, X is O or S, m is 2 or 3, and n is 1, or is 2 if R1=R2=H and X=O. Polymerization can be effected in bulk, solution, emulsion or suspension using as catalysts organic peroxides, azo compounds, boron trifluoride, sulphur dioxide, stannic chloride or aluminium chloride. The compounds may be copolymerised with acrylic and methacrylic acids, esters, amides and nitriles; esters of maleic, fumaric, itaconic and citraconic acids; vinyl and vinyloxyalkyl carboxylates; vinyl alkyl and hydroxyalkyl ethers; vinyl and vinylidene halides; acetoxybutadiene; ethylene, styrene and divinylbenzene; ethylene diacrylate and dimethacrylate; vinyloxyalkyl acrylates; bis-(vinyloxyethyl)-urea. The monomers or polymers which contain an -NH,CX,NH-grouping form methylol derivatives by treatment with formaldehyde and these can be acid-condensed to methylene-bis-compounds. Infusible products are also obtained by further heating the methylol-free polymers. The sulphide group in the monomers can be oxidised to a sulphoxide or sulphone group, in which case polymerization is carried out with an anionic or basic catalyst, e.g. sodamide, potassamide or a lithium alkyl. Examples show the polymerization of N-ethyl-N1-methyl-N1-2-(vinylthio)-ethyl-urea, N1-methyl-N1-2-(vinylthio) -ethyl-morpholine-N-carboxamide and N-octadecyl-N1-2-(vinylthio)-propyl-urea, and the preparation of the following copolymers:- (1) N-ethyl-N1-methyl-N1-2-(vinylthio)-ethyl-urea or N1-methyl-N1-2-(vinylthio) -ethyl-morpholine-N-carboxamide with methyl methacrylate or acrylonitrile, the latter giving spinnable fibres; and (2) N-octadecyl-N1-methyl-N1-2-(vinylthio)-ethyl-thiourea with butyl acrylate. It is also stated that hexamethylene-bis-(N1methyl-N1-2-(vinylthio) -ethyl-urea) can be copolymerised with formamidoethyl vinyl ether, ureidoethyl vinyl ether, vinyloxyethyl-ethylene-urea, allyl carbamate, styrene, vinyl acetate, acrylonitrile, acrylates and methacrylates. The polymers and copolymers (including methylolated derivatives) are useful additives to cellulose acetate or cellulose acetate-butyrate spinning dopes, the polymer of N-ethyl-N1-methyl-N1-2-(vinylthio)-ethyl-urea being mentioned for this purpose.ALSO:The invention comprises compounds of the following formulae:-I : CH2 = CH.S.#j(NHCX)n NR1R2; II: CH2 = CH.S.A.NR3.CX.NR1R2; III;(CH2 = CH.S.#j.NH.CX.NH)mR4;IV:(CH2 = CH.S.A.NR3.CX.NH)mR4, where A is C2-C6 alkylene, #j is o- or p-phenylene optionally monoor disubstituted by C1-C4 alkyl, R1 is H, C1-C18 alkyl, alkenyl, cycloalkyl, aralkyl, aryl or chloroaryl, R2 is H, methyl or ethyl (or NR1R2 is a morpholino, piperidino or pyrrolidino residue), R3 is H or C1-C4 alkyl, R4 is C4-C10 alkylene, phenylene, tolylene, methylene-bis-phenylene, methylidyne-tris-phenylene or dianisylene, X is O or S, m is 2 or 3, and n is 1, or 2 if R1 = R2 = H and X = O. Compounds I where n is 2 and X is O are made by treating amines CH2 = CH.S.#j.NH2 with an alkali metal cyanate and a mineral acid. Compounds I and II where R1 but not R2 is H are made from the corresponding amines and R2NCO or R2NCS. Compounds I and II where both R1 and R2 are other than H are obtained from the amines and R1R2 NCX.halogen. Compounds II where R1 and R2 are both H are prepared from the amines and an alkali metal cyanate or thiocyanate with a mineral acid, or by fusing the amines with urea or thiourea, this latter method also serving for compounds I where n is I, X is S and R1 and R2 are both H. Compounds III and IV are made from the amines and the appropriate di- or tri-isocyanate or -isothiocyanate. The sulphide group in the products can be oxidised to the corresponding sulphoxides and sulphones and can add mercaptans in the b -position to give di-sulphides. Those which have a -NH.CX.NH- grouping also react with aldehydes, especially formaldehyde to give methylol derivatives which can be further condensed to methylene-bis-compounds. Examples show the preparation of the following: (1) 2-ureidoethyl vinyl sulphide from 2-aminoethyl vinyl sulphide with potassium cyanate and acid or by heating with urea; (2) the N-methyl derivative of (1) by the cyanate method; (3) N : N1-disubstituted ureas from 2-(N-methylamino)-ethyl vinyl sulphide with ethyl and octadecyl isocyanates respectively; (4) 2-(vinylthio)-phenyl-biuret from 2-aminophenyl vinyl sulphide with potassium cyanate and acid; (5) a disubstituted urea from 2-aminophenyl vinyl sulphide and ethyl isocyanate; (6) a disubstituted urea from 3-aminopropyl vinyl sulphide and dimethylcarbamyl chloride; (7) an amide from 2-(N-methylamino)-ethyl vinyl sulphide and morpholine-N-carboxylic chloride; (7) a disubstituted thiourea from 2-aminoethyl vinyl sulphide and phenyl isothiocyanate; (8) a disubstituted thiourea from 2-(N-methylamino)-ethyl vinyl sulphide and t-octyl isothiocyanate; (a) bis-ureas from 2-(N-methylamino)-ethyl sulphide and hexamethylene di-isocyanate and diphenylmethane-4 : 41-di-isocyanate respective; (10) 2-thioureidoethyl vinyl sulphide by heating 2-aminoethyl vinyl sulphide with thiourea. Other suitable starting materials are mentioned in which A may also be propylene or isobutylene, #j may be p-phenylene, tolylene or xylylene, R1 may be propyl, isopropyl, butyl, isobutyl, t-butyl, amyl, isoamyl, hexyl, decyl, dodecyl, hexadecyl, oleyl, cyclohexyl, chlorophenyl, naphthyl or benzyl, R2 may be ethyl, R3 may be butyl and R4 may be tetramethylene, decamethylene, tolylene, dianisylene and methylidyne-tris-phenylene. N : N1-bis-(2-vinylthioethyl)-urea is obtained by heating 2-aminoethyl vinyl sulphide with urea. Aminoalkyl and aminoaryl vinyl sulphides unsubstituted on the N-atom are made from the corresponding mercaptans and acetylene with a basic catalyst. Alkylaminoalkyl vinyl sulphides are obtained by reacting thiourea with an alkylaminoalkyl halide and treating the resulting isothiouronium salt with acetylene. Specification 747,184 is referred to.ALSO:A compound of one of the formulae specified below is applied to wool from aqueous or alcoholic solution to react with the SH groups of the wool; the wool is then heated with formaldehyde and an acid catalyst, whereby the hand and stiffness are modified and shrinkage is reduced. Also, one of the compounds can be N-methylolated and applied to textiles (especially cellulosic or glass fibre) to provide anchoring sites for subsequent reagents. Polymers and copolymers of these compounds also give reduced shrinkage on woollen and cellulosic fabrics. The four types of compounds are CH2=CH,S,#j(NHCXn) NR1R2, CH2=CH,S,A,NR3,CX,NR1R2, (CH2=CH,S,#j,NH,CX,NH)mR4 and (CH2=CH,S,A,NR3,CX,NH)mR4, where A is C2-C6 alkylene, #j is o- or p-phenylene optionally mono- or disubstituted by C1-C4 alkyl, R1 is H,C1-C18 alkyl, alkenyl, cycloalkyl, aralkyl, aryl or chloroaryl, R2 is H, methyl or ethyl (or NR1R2 is a morpholino, piperidino or pyrrolidino residue), R3 is H or C1-C4 alkyl, R4 is C4-C10 alkylene, phenylene, tolylene, methylene-bis-phenylene, methylidyne-tris-phenylene or dianisylene, X is O or S, m is 2 or 3, and n is 1, or is 2 if R1=R2=H and X=0. It is stated in particular that the polymer of N-octadecyl-N1-2-(vinylthio)-propyl-urea imparts a soft hand to fabrics.ALSO:Materials for coating comprise polymers and copolymers of compounds of one of the following formulae, including N - methylol derivatives which become cross-linked on heating: CH2=CH.S.#f(NHCX)nNR1R2, CH2=CH.S.A.NR3.CX.NR1R2, (CH2=CH.S.#f.NH.CX.NH)mR4 and (CH2=CH.S.A.NR3.CX.NH)mR4, where A is C2-C6 alkylene, #f is o- or p-phenylene optionally mono- or disubstituted by C1-C4 alkyl, R1 is H, C1-C18 alkyl, alkenyl, cycloalkyl, aralkyl, aryl or chloroaryl, R2 is H, methyl or ethyl (or NR1R2 is a morpholino, piperidino or pyrrolidino residue), R3 is H or C1-C4 alkyl, R4 is C4-C10 alkylene, phenylene, tolylene, methylene-bis-phenylene, methylidynetris-phenylene or dianisylene, X is O or S m is 2 or 3, and n is 1, or is 2 if R1=R2=H and X is O. In an example, metal panels are treated with a solution of a copolymer of methyl methacrylate and N-ethyl-N1-methyl-N1-2vinylthio)-ethyl-urea in ethoxyethyl acetate with the addition of titanium dioxide, and then baked; there may also be present ureaformaldehyde-butanol condensates and acids such as butyl acid phthalate; the panels can also be glass or ceramic. A polymer of N1methyl - N1 - 2 - (vinylthio) - ethyl - morpholineN-carboxamide is also stated to be useful as a coating material.ALSO:Fungicidal compositions for plants comprise solutions in high-flash naphtha of compounds of one of the following formulae = CH2 = CH,S,#F (NHCX)n NR1R2, CH2 = CH,S,NR3,CX, NR1R2, (CH2 = CH,S,#F,NH,CX,NH)m R4 and (CH2 = CH,S,A,NR3,CX,NH)m R4, where A is C2-C6 alkylene, #F is o- or p-phenylene optionally mono- or di-substituted by C1-C4 alkyl, R1 is H, C1-C18 alkyl, alkenyl, cycloalkyl, aralkyl, aryl or chloroaryl, R2 is H, methyl or ethyl (or NR1R2 is a morpholino, piperidino or pyrrolidino residue), R3 is H or C1-C4 alkyl, R4 is C4-C1 alkylene, phenylene, tolylene, methylene-bis-phenylene, methylidyne-tris-phenylene or dianisylene, X is O or S m is 2 or 3, and n is 1 or 2 if R1 R2 = H and X = O. Particular compounds mentioned are N-phenyl-N1-2-(vinylthio)-ethyl thiourea and N-t-octyl-N1-methyl-N1-(2-vinylthio)-ethyl thiou

  本发明涉及以下化合物的聚合物和共聚物：-I：CH2 = CH，S，#j（NHCX）nNR1R2；II：CH2 = CH，S，A，NR3，CX，NR1R2；III：（CH2 = CH.S.#j.NH.CX.NH）mR4；IV：（CH2 = CH.S.A.NR3.CX.NH）mR4，其中A是C2-C6烷基，#j是o-或p-苯基，可选择单或双取代C1-C4烷基，R1是H，C1-C18烷基，烯基，环烷基，芳基或氯芳基，R2是H，甲基或乙基（或NR1R2是吗啡啉，哌啶或吡咯啉残基），R3是H或C1-C4烷基，R4是C4-C10烷基，苯基，甲苯基，亚甲基-双苯基，甲基亚苯基或二苯基甲烷，X是O或S，m为2或3，n为1，或者如果R1 = R2 = H且X = O，则为2。可以使用有机过氧化物，偶氮化合物，三氟化硼，二氧化硫，三氯化锡或氯化铝作为催化剂，在块状，溶液，乳液或悬浮液中进行聚合。这些化合物可以与丙烯酸和甲基丙烯酸，酯，酰胺和腈共聚；马来酸，富马酸，异柠檬酸和柠檬酸酯的酯；乙烯和乙烯基氧基烷基羧酸酯；乙烯基烷基和羟基烷基醚；乙烯和乙烯基卤化物；乙酰基丁二烯；乙烯，苯乙烯和二乙烯基苯；乙二酸乙烯酯和二甲基丙烯酸酯；乙烯氧基丙烯酸酯；双（乙烯氧基乙基）脲。含有-NH，CX，NH-基团的单体或聚合物通过与甲醛处理形成甲醇衍生物，这些甲醇衍生物可以酸缩成亚甲基双化合物。无法熔融的产品也可通过进一步加热无甲醇聚合物获得。单体中的硫化物基团可以氧化为硫氧化物或磺酸基团，在这种情况下，聚合是用阴离子或碱性催化剂进行的，例如氢化钠，氢化钾或锂烷基。示例显示了N-乙基-N1-甲基-N1-2-（乙烯硫基）-乙基脲，N1-甲基-N1-2-（乙烯硫基）-乙基吗啡啉-N-羧酰胺和N-十八烷基-N1-2-（乙烯硫基）-丙基脲的聚合，以及以下共聚物的制备：（1）N-乙基-N1-甲基-N1-2-（乙烯硫基）-乙基脲或N1-甲基-N1-2-（乙烯硫基）-乙基吗啡啉-N-羧酰胺与甲基丙烯酸甲酯或丙烯腈共聚，后者可产生可纺织的纤维；以及（2）N-十八烷基-N1-甲基-N1-2-（乙烯硫基）-乙基硫脲与丁基丙烯酸酯。还说明了已六亚甲基双（N1-甲基-N1-2-（乙烯硫基）-乙基脲）与甲酰乙基乙烯醚，尿素乙烯醚，乙烯-脲基乙烯醚，丙烯酸烯丙酯，苯乙烯，乙酸乙烯酯，丙烯腈，丙烯酸酯和甲基丙烯酸酯共聚的聚合物。这些聚合物和共聚物（包括甲醇化衍生物）是纤维素醋酸或纤维素醋酸丁酸纺丝液的有用添加剂，其中N-乙基-N1-甲基-N1-2-（乙烯硫基）-乙基脲的聚合物被提及用于此目的。此外，本发明还涉及以下化合物：I：CH2 = CH.S.#j（NHCX）nNR1R2；II：CH2 = CH.S.A.NR3.CX.NR1R2；III：（CH2 = CH.S.#j.NH.CX.NH）mR4；IV：（CH2 = CH.S.A.NR3.CX.NH）mR4，其中A是C2-C6烷基，#j是o-或p-苯基，可选择单或双取代C1-C4烷基，R1是H，C1-C18烷基，烯基，环烷基，芳基或氯芳基，R2是H，甲基或乙基（或NR1R2是吗啡啉，哌啶或吡咯啉残基），R3是H或C1-C4烷基，R4是C4-C10烷基，苯基，甲苯基，亚甲基-双苯基，甲基亚苯基或二苯基甲烷，X是O或S，m为2或3，n为1，或者如果R1 = R2 = H且X = O，则为2。化合物I，其中n为2且X为O，是通过用碱金属氰酸盐和矿物酸处理胺CH2 = CH.S.#j.NH2制备的。化合物I和II，其中R1但不是R2为H，是从相应的胺和R2NCO或R2NCS制备的。化合物I和II，其中R1和R2都不是H，是从胺和R1R2 NCX.卤素制备的。化合物II，其中R1和R2都是H，是通过用矿物酸处理的氰酸盐或硫氰酸盐和胺融合而成的，这种方法也用于化合物I，其中n为I，X为S，R1和R2都是H。化合物III和IV是从胺和适当的二或三异氰酸酯或-异硫氰酸酯制备的。这些产品中的硫化物基团可以氧化为相应的硫氧化物和磺酸基团，并且可以添加巯基在b-位置上形成二硫化物。其中具有-NH.CX.NH-基团的化合物还与醛反应，特别是与甲醛反应形成甲醇衍生物，这些甲醇衍生物可以进一步缩合成亚甲基双化合物。示例显示了以下的制备：（1）从2-氨基乙基乙烯硫醚与氰酸钾和酸或与尿素加热制备2-尿素基乙基乙烯硫醚；（2）通过氰酸盐法制备（1）的N-甲基衍生物；（3）从2-（N-甲基氨基）-乙基乙烯硫醚分别与乙酰基异氰酸酯和十八烷基异氰酸酯反应制备N：N1-二取代脲；（4）从2-氨基苯基乙烯硫醚与氰酸钾和酸制备2-（乙烯硫基）-苯基双脲；（5）从2-氨基苯基乙烯硫醚和乙酰基异氰酸酯制备双取代脲；（6）从3-氨基丙基乙烯硫醚和二甲基氨基甲酰氯制备双取代脲；（7）从2-（N-甲基氨基）-乙基乙烯硫醚和吗啡啉-N-羧酸氯制备酰胺；（7）从2-氨基乙基乙烯硫醚和苯基异硫氰酸酯制备双取代硫脲；（8）从2-（N-甲基氨基）-乙基乙烯硫醚和t-辛基异硫氰酸酯制备双取代硫脲；（a）从2-（N-甲基氨基）-乙硫醚和己二酸二异氰酸酯和二苯甲烷-4：41-二异氰酸酯分别制备双脲；（10）通过加热2-氨基乙基乙烯硫醚和硫脲制备2-硫脲基乙基乙烯硫醚。还提到了其他适合的起始材料，其中A也可以是丙烯或异丁烯，#j可以是p-苯基，甲苯基或二甲苯基，R1可以是丙基，异丙基，丁基，异丁基，叔丁基，戊基，异戊基，己基，癸基，十二烷基，十六烷基，油酸基，环己基，氯苯基，萘基或苄基，R2可以是乙基，R3可以是丁基，R4可以是四亚甲基，十碳烷基，甲苯基，二甲苯基和亚甲基三苯基。N：N1-双（2-乙烯硫基乙基）-脲是通过加热2-氨基乙基乙烯硫醚和尿素制备的。未在N-原子上取代的氨基烷基和氨基芳基乙烯硫醚可由相应的巯基和乙炔与碱性催化剂反应制备。通过将硫脲与烷基氨基烷卤化物反应并用乙炔处理产生的异硫脲氢盐制备烷基氨基烷基乙烯硫醚。参见规范747,184。此外，本发明还涉及以下化合物：CH2 = CH，S，#j（NHCX）nNR1R2；CH2 = CH，S，A，NR3，CX，NR1R2；（CH2 = CH.S.#j.NH.CX.NH）mR4；（CH2 = CH.S.A.NR3.CX.NH）mR4，其中A是C2-C6烷基，#j是o-或p-苯基，可选择单或双取代C1-C4烷基，R1是H，C1-C18烷基，烯基，环烷基，芳基或氯芳基，R2是H，甲基或乙基（或NR1R2是吗啡啉，哌啶或吡咯啉残基），R3是H或C1-C4烷基，R4是C4-C10烷基，苯基，甲苯基，亚甲基-双苯基，甲基亚苯基或二苯基甲烷，X是O或S，m为2或3，n为1，或者如果R1 = R2 = H且X = O，则为2。将其中一种化合物从水或酒精溶液中施加到羊毛上，以与羊毛的SH基团反应；然后用甲醛和酸催化剂加热，从而改变手感和硬度，并减少收缩。此外，可以将其中一种化合物N-甲基化并应用于纺织品（特别是纤维素或玻璃纤维），以提供用于后续试剂的锚定位点。这些化合物的聚合物和共聚物还可在羊毛和纤维素织物上减少收缩。这些化合物的四种类型是CH2 = CH，S，#j（NHCXn）NR1R2，CH2 = CH，S，A，NR3，CX，NR1R2，（CH2 = CH，S，#j，NH，CX，NH）mR4和（CH2 = CH，S，A，NR3，CX，NH）mR4，其中A是C2-C6烷基，#j是o-或p-苯基，可选择单或双取代C1-C4烷基，R1是H，C1-C18烷基，烯基，环烷基，芳基或氯芳基，R2是H，甲基或乙基（或NR1R2是吗啡啉，哌啶或吡咯啉残基），R3是H或C1-C4烷基，R4是C4-C10烷基，苯基，甲苯基，亚甲基-双苯基，甲基亚苯基或二苯基甲烷，X是O或S，m为2或3，n为1，或者如果R1 = R2 = H且X = O，则为2。特别提到N-十八烷基-N1-2-（乙烯硫基）-丙基脲的聚合物赋予织物柔软的手感。此外，本发明还涉及以下化合物的聚合物和共聚物：CH2 = CH，S，#f（NHCXn）NR1R2，CH2 = CH，S，A，NR3，CX，NR1R2，（CH2 = CH，S，#f，NH，CX，NH）mR4和（CH2 = CH，S，A，NR3，CX，NH）mR4，其中A是C2-C6烷基，#f是o-或p-苯基，可选择单或双取代C1-C4烷基，R1是H，C1-C18烷基，烯基，环烷基，芳基或氯芳基，R2是H，甲基或乙基（或NR1R2是吗啡啉，哌啶或吡咯啉残基），R3是H或C1-C4烷基，R4是C4-C10烷基，苯基，甲苯基，亚甲基-双苯基，甲基亚苯基或二苯基甲烷，X是O或S，m为2或3，n为1，或者如果R1 = R2 = H且X = O，则为2。在一个例子中，用甲基丙烯酸甲酯和N-乙基-N1-甲基-N1-2-（乙烯硫基）-乙基脲的共聚物的乙氧基乙酸酯溶液加入二氧化钛处理金属板，然后烘烤；还可以存在尿素甲醛-丁醇缩合物和酸，例如丁酸邻苯二甲酸酯；板还可以是玻璃或陶瓷。N1-甲基-N1-2-（乙烯硫基）-乙基吗啡啉-N-羧酰胺的聚合物也被认为是一种有用的涂料材料。此外，本发明还涉及以下化合物：CH2 = CH，S，#f（NHCXn）NR1R2，CH2 = CH，S，A，NR3，CX，NR1R2，（CH2 = CH，S，#f，NH，CX，NH）mR4和（CH2 = CH，S，A，NR3，CX，NH）mR4，其中A是C2-C6烷基，#f是o-或p-苯基，可选择单或双取代C1-C4烷基，R1是H，C1-C18烷基，烯基，环烷基，芳基或氯芳基，R2是H，甲基或乙基（或NR1R2是吗啡啉，哌啶或吡咯啉残基），R3是H或C1-C4烷基，R4是C4