聚（乙烯胺）类似物的声明，以 Federal lav 联邦低 Sponsored Research This invention was made with Government support under grant number DMR-9350473 and grant number DMR- 9634528 awarded by the National Science Foundation.赞助的研究发明，这是与政府的支持下，授权号码，移民和难民事务部- 9350473和授权号码，移民和难民事务部- 9634528颁发的国家科学基金会。 The Government has certain rights in the invention.政府的某些权利的发明。

Backaround of the Invention This invention relates to the formation of vinyl amine derivatives and their polymerization to form new poly(vinyl amine) analogs. backaround的发明，这项发明涉及到的形成，乙烯胺衍生物及其聚合形成新的聚（乙烯胺）类似物。

Poly(vinyl amine) and its analogs are members of an important class of cationic polyelectrolytes, which are very desirable materials with applications in the textile, adhesive and coatings, paper, petroleum, water treatment, cosmetic, and pharmaceutical industries.聚（乙烯胺）及其类似物的成员，一个重要的类阳离子聚电解质，这是非常可取的材料应用在纺织，粘合剂和涂料，造纸，石油，水处理，化妆品，工业和制药工业。

However, poly(vinyl amine) analogs cannot be obtained through the polymerization of the obvious parent molecule, vinyl amine, because vinyl amine is unstable with respect to its imine tautomer, ethylimine.然而，聚（乙烯胺）类似物不能获得通过聚合明显的母公司分子，乙烯胺，因为乙烯胺是不稳定与尊重其亚胺互变异构体， ethylimine 。

Poly(vinyl amine) analogs therefore have been obtained by indirect methods, eg, th Hofmann rearrangement of poly(acrylamide) or the Schmidt reaction of poly(acrylic acid).聚（乙烯胺）类似物，因此已获得的间接方法，例如，钍Hofmann重排聚（丙烯酰胺） ，或施密特反应的聚（丙烯酸） 。

Summarv summarv of the Invention The invention is based on the discovery that new poly(vinyl amine) analogs can be prepared by polymerization of precursors obtained by the isomerization of allylamines, allylamides, or allylimides.该发明的发明是基于发现新的聚（乙烯胺）类似物，可以编写的聚合体获得的异构化反应的allylamines ， allylamides ，或allylimides 。 New copolymers can also be formed using the same precursors in combination with other polymerizable substrates.新的共聚物也可以形成使用相同的前体的组合与其他聚合基板。 These new polymers and copolymers are polyelectrolytes, bearing side chains which become positively charged at low pH.这些新的聚合物和共聚物是聚电解质，同时侧链成为带正电荷，在低pH值。 Furthermore, the new此外，新 methods require fewer steps than methods previously employed to obtain poly(vinyl amines).方法需要较少的步骤，方法比以前受聘取得聚（乙烯胺） 。

In general, the invention features a polymer在一般的发明，功能高分子 having the formula (1):有公式（ 1 ） ： where R1 through R4, independently, are hydrogen; an alkyl, eg, R1的情况下，通过R4的，独立的，是氢气;一烷基，例如， CaH2a+lt cah2a +审裁处 where a is 1 to 20 or higher; an aryl, eg, phenyl or substituted phenyl, eg, substituted with CH3, CF3, or OCH3; an acyl, eg, COH, COCH3, or COCF3; or a halogen, eg, F, C1, Br, or I; R5 and R6, independently can be hydrogen; alkyl; aryl; acyl; alkoxycarbonyl, eg, COOCH3, COOC(CH3)3, or COOCH2CH3; or silyl, eg, Si(CH3)3, (CH3)2SiC(CH3)3 or Si(CH(CH3)2)3; and n is at least 2.如果是1至20或更高版本;一芳，例如，苯基或取代苯基，例如，取代甲基， cf3 ，或och3 ;一酰基，例如， coh ， coch3 ，或cocf3 ;或一卤素，例如，男，的C1 ，溴，或者我; R5的和r6 ，独立可氢气;烷基;芳;酰基; alkoxycarbonyl ，例如， cooch3 ， cooc （甲基） 3 ，或cooch2ch3 ;或含硅，例如，在Si （甲基） 3 ， （甲基） 2sic （甲基）三或四型（ CH （甲基） 2 ） 3 ; N是至少2 。 n can be up to 10,000, 100,000, 1,000,000, or higher. n最多可以有一万，十万，百万，或更高。

In some cases, R1, R2, R3, and R4 are all hydrogen to give a polymer having formula (2).在某些情况下， R1的， R2的， R3的，和R4都是氢气，使聚合物后，公式（ 2 ） 。

R5 also can be hydrogen, and R6 can be an acyl, forming a poly(crotyl amide). R5的也可以氢， r6可以是一个酰基，形成了聚（ crotyl酰胺） 。 Some specific examples include poly(crotyl formamide), poly(crotyl acetamide), poly (crotyl dichloroacetamide), poly (crotyl一些具体的例子包括聚（ crotyl甲酰胺） ，聚（ crotyl乙酰胺） ，聚（ crotyl dichloroacetamide ） ，聚（ crotyl trichioroacetamide), trichioroacetamide ） ， and poly(crotyl trifluoroacetamide).和聚（ crotyl trifluoroacetamide ） 。

Alternatively, R5 and R6 both can be acyl, forming a poly(crotyl imide).另外， R5的和r6都可以酰基，形成了聚（ crotyl酰亚胺） 。 In addition, R5 and R6 can be attached to each other to form a ring structure, as in poly(crotyl N-succinimide) having formula (3).在此外， R5的和r6可以附在对方，以形成一个环形结构，在聚（ crotyl的N -丁二）有公式（ 3 ） 。

Another aspect of the invention is a method for preparing a polymer by obtaining and then subjecting to polymerization conditions, a vinylic monomer having formula (4), where R1 to R6 are as defined above.另一个方面的发明，是一个法制备聚合物获取，然后服从，以聚合条件， vinylic单体后，公式（ 4 ） ，其中R1的，以r6是如上所确定的。

The monomer can be prepared by isomerization of the allylic species with the formula (5).单体可以编写的异构化反应的烯丙基物种与公式（ 5 ） 。

Polymerization methods include, but are not limited to, those described in the detailed description.聚合方法包括，但不仅限于，这些描述的详细描述。

In another aspect, the invention features a copolymer having the formula (6):在另一个方面，该发明具有共聚物具有公式（ 6 ） ： wherein the repeating units (7) and (8) can be linked in any其中重复单位（ 7 ） （ 8 ）可以挂在任何 order and in any orientation, eg, the unit (7) can be repeated several times in the copolymer chain before a unit (8) occurs, and vice versa.为了和在任何方向，例如，单位（ 7 ）可以反复多次在共聚物链的前一个单位， （ 8 ）发生，反之亦然。 R1 to R6 are defined as above; R7 and R1的，以r6被界定为以上; r7和 Rg, 的RG ， independently, are hydrogen, alkyl, aryl, acyl, or halogen.独立，是氢，烷基，芳基，酰基，或卤素。 R8 and r8和 R10, 奥迪R10 V型12 ， independently, are hydrogen, alkyl, aryl, acyl,独立，是氢，烷基，芳基，酰基， NRllRl2 nrllrl2 OCOR11, ocor11 ， CONR11R12, conr11r12 ， CO2, 二氧化碳， CN,架CN ， COOR11, coor11 ， or NR11COR12; where R11 and R12, independently, are hydrogen, alkyl, aryl, acyl, or silyl.或nr11cor12 ;而设计，和r12 ，独立，是氢，烷基，芳基，酰基，或含硅。

n is at least 2. n是至少2 。 n can be up to 10,000, 100,000, 1,000,000, or higher. n最多可以有一万，十万，百万，或更高。

In certain examples, the copolymer has the formula在某些例子中，共聚物有公式 where X can be O or NR13; where R13 can be hydrogen, alkyl, aryl, silyl, or其中X可以O或nr13 ;何处r13可以氢，烷基，芳基，含硅，或 ac 交流 In certain other examples, R7 and在某些其他的例子， r7和 Rg 的RG are hydrogen.是氢气。

In another aspect, the invention features a method for preparing a copolymer from monomers having the formulae (10) and (11), where R1 to在另一个方面，发明特点的方法，准备从单体的共聚物具有公式（ 10 ）及（ 11 ） ，其中R1的要 Rlo rlo are as defined above, by subjecting these monomers to polymerization conditions.是如上所确定的，受到这些单体以聚合条件。

Monomer (11) can be, for example, maleic anhydride; maleimide; an N-alkyl maleimide, eg, N-butyl maleimide; an N-aryl maleimide, eg, N-xylyl maleimide; an N-silyl maleimide, eg, N-trimethylsilyl maleimide; or an N-acyl maleimide, eg, N-pivaloyl maleimide.单体（ 11 ）可以，例如，顺丁烯二酸酐;酰亚胺;一N -烷基酰亚胺，例如， N -丁基马来酰亚胺; N -芳基酰亚胺，例如， N -二xylyl酰亚胺;的N -含硅酰亚胺，例如， n -三甲基硅酰亚胺;或一N -酰基酰亚胺，例如， N -二pivaloyl马来。

Alternatively, monomer (11) can be, for example, a vinylic amine, a vinylic ester, a vinylic amide, a vinylic carboxylate, or a vinylic nitrile.另外，单体（ 11 ）可以，例如， vinylic胺，一vinylic酯， vinylic酰胺，一vinylic羧酸，或一vinylic腈。

Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.除非另有界定，所有的技术和科学术语，此处使用的具有相同的含义，作为普遍的理解，一个普通的技能，在艺术，这是属于发明。 Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, the preferred methods and materials are described below.虽然方法和材料，类似或相等于那些此处所述，可用于在实践中或测试本发明，首选的方法和材料，叙述如下。 All publications, patent applications, patents, and other references mentioned herein are incorporated by reference in their entirety.所有出版物，专利申请，专利和其他参考此处提及的是通过提及而纳入他们的全部内容。 In case of conflict, the present application, including definitions, will control.在冲突的情况下，目前的应用，包括定义，将控制。 In addition, the materials, methods, and examples are illustrative此外，该材料，方法和例子是说明性 xnly xnly and not intended to be limiting.和不打算限制。

An advantage of the new methods is the utilization of easily accessible allylic amine derivatives as monomer precursors.一，利用这种新方法是利用方便烯胺衍生物作为单体的前体。 Allylic amine derivatives are inexpensive to prepare and are very stable.烯胺衍生物是廉价的准备，而且非常稳定。 The facile isomerization described herein provides the reactive vinyl amine derivatives necessary for polymerization.该简易异构化此处所述的规定，无功乙烯胺衍生物所必需的聚合。

The polymers of the invention are unique in that they include not only the amine functionality attached at every other carbon atom along the polymer backbone, conferring polyelectrolytic properties, but also an alkyl or alkyl derivative attached to the intervening carbon atoms of the backbone.聚合物的发明是独一无二的，因为它们不仅包括胺的功能附加在每一个其他的碳原子沿聚合物的骨干，赋予polyelectrolytic性能，而且还一烷基或烷基衍生的重视中间碳原子的骨干。 In the parent poly(vinyl amine),在家长聚（乙烯胺） ， this position is simply occupied by a hydrogen atom.这一立场是简单地被占领的一个氢原子。

This allows for tremendous diversity in the realm of poly(vinyl amine) derivatives.这使得巨大的多样性的境界聚（乙烯胺）的衍生物。 For example, a lipophilic group at this locus can be used to create phase transfer catalysts or even hydrocarbon soluble polyelectrolytes.例如，亲脂性组在这个轨迹可以用来建立相转移催化剂，甚至烃类可溶性聚电解质。

Other features and advantages of the invention will be apparent from the following detailed description, and from the claims.其他的特点和优势的发明，将明显从下面的详细描述，并从索赔。

Detailed Description The isomerization and subsequent polymerization of allylamines, allylamides, and allylimides yields new polymers belonging to the family of poly(vinyl amine) analogs.详细描述异构化和随后的聚合allylamines ， allylamides ， allylimides产量新的聚合物，属于家庭的聚（乙烯胺）类似物。 By combining the intermediate isomerization products with other polymerizable molecules, new copolymers are also obtained.相结合的中间异构化的产品与其他聚合分子，新的共聚物，也得到了。 Since the side chains on the polymers bear nitrogen atoms with an unshared electron pair, the polymers become protonated in acidic solution to generate polycationic species.由于侧链对聚合物承担氮原子与一取消共用电子对，聚合物成为质子在酸性溶液中产生polycationic物种。 The new methods allow a wide range of poly(vinyl amine) analogs to be obtained in few steps, as the allylic precursors are readily available.新方法允许范围广泛的聚（乙烯胺）类似物，以获得在几个步骤，作为烯前体是现成的。

Prenaration prenaration of Monomers Three classes of substrates can be used to form stable or transient vinyl amine analogs upon isomerization: allylamines, allylamides, and allylimides.单体三类基板可以用来形成稳定的或短暂的乙烯胺类似物后，异构化： allylamines ， allylamides ， allylimides 。 These substrates are catalytically isomerizable to enamines, enamides, and enimides, respectively, all of which are structurally similar to either vinyl amine or the protected vinyl amine monomer.这些基板催化isomerizable ，以enamines ， enamides ， enimides ，分别是，所有这一切都是在结构上类似要么乙烯胺或受保护的乙烯胺单体。

In the following description, primary enamines, alkyl enamines, and aryl enamines are called unprotected monomers.在下面的说明，主要enamines ，烷基enamines ，和芳enamines是所谓的未受保护的单体。 Enamides (acyl enamines), enimides (diacyl enamides （酰基enamines ） ， enimides （二酰基 enamines), vinylic carbamates (alkoxycarbonyl enamines), and silyl enamines are protected monomers. enamines ） ， vinylic氨基甲酸酯（ alkoxycarbonyl enamines ） ，含硅enamines保护单体。

Unprotected Monomers Enamines offer the most direct approach to the preparation of vinyl amine-derived copolymers.未受保护的单体enamines提供最直接的方法来制备乙烯胺衍生共聚物。 The polymerization of these compounds incorporates an amine functionality into the polymer without the need for deprotection of a precursor.聚合这些化合物包含一胺的功能，到聚合物，而不需要脱一个前兆。 Depending on the amine substitution, however, an enamine can be unstable with respect to its imine form.根据对胺替代，不过，一enamine可以不稳定与尊重其亚胺形式。 Generally, less substituted enamines, eg, primary enamines, are less stable than their more substituted relatives.一般来说，少取代enamines ，例如，小学enamines ，较差的稳定比他们更取代的亲属。 Hence, less substituted monomers are most amenable to copolymerization.因此，少取代单体是最适合共聚。

Secondary and tertiary enamines have alkyl or aryl substituents, eg, ethyl, isobutyl, phenyl or substituted phenyls.中学及大专enamines有烷基或芳基取代，例如，乙基，异丁基，苯基或取代phenyls 。 These substituents help to stabilize the monomers with respect to the unsubstituted vinyl amines.这些取代基有助于稳定单体方面向unsubstituted乙烯胺。

A number of routes lead to tertiary enamines, including isomerization.一些路线导致高等教育enamines ，包括异构化。 For example, many tertiary allylamines isomerize to例如，许多大专allylamines isomerize ，以 tertiary 大专 enamines using a catalyst. enamines使用的催化剂。 Examples of例子 isomerization 异构化 catalysts include those derived from ruthenium, eg, 10 mol%催化剂包括那些来自钌，例如， 10 mol ％时 RuClH(CO) (PPh3) ruclh （合作） （ pph3 ） in ref fluxing benzene for 1 to 15 hours; cobalt, eg, 1 mol% CoH(N2)(PPh3) in在参熔合苯为1至15小时;钴，例如， 1 mol ％时coh （氮气） （ pph3 ）在 tetrahydrofuran 四氢呋喃 (THF) at 800C for 15 hours; rhodium, eg, 1 mol% （四氢呋喃）在800c为15小时;铑，例如， 1 mol ％时 [Rh(diphosphine)(THF)n]+~Cl04 [铑（膦） （四氢呋喃） N的] + 〜 cl04 in THF at 400C for 23 hours, the diphosphine ligand can be 2,2'-在THF在400c为23小时，双膦配体可以2,2 ' - bis(diphenylphosphino)-l,l'-binaphthyl 双（二苯膦基） -升的L' -联萘 (BINAP); or molybdenum, eg, 1 mol% trans-Mo(N2)(Ph2PCH2CH2PPH2)2 in toluene at 1000C for 1.5 to 5 hours. （ binap ） ;或钼，例如， 1 mol ％与跨钼（氮气） （ ph2pch2ch2pph2 2 ）在甲苯在1000c为1.5至5小时。

Alternatively, the isomerization can be catalyzed by base.此外，异构化，可催化基地。 Representative examples of basic catalyts代表性的例子基本catalyts include potassium tert-butoxide or potassium amide on alumina.包括钾叔butoxide或钾酰胺对氧化铝。

Secondary enamines are less stable than tertiary enamines and tend to tautomerize to the corresponding imines, although the isomerization of secondary allylamines with a ruthenium catalyst allows selective, transient formation of secondary enamines.中学enamines较差的稳定比大专enamines ，且往往tautomerize到相应的亚胺，虽然异构化中学allylamines与钌催化剂允许有选择性的，短暂的形成，中学enamines 。 For these compounds, it is necessary to polymerize the intermediate species before tautomerization, eg, at low temperature, eg, -1000C to 1000C, and preferably -100C to 250C, and under anhydrous conditions, to produce vinyl amine polymers.对于这些化合物，这是必要的聚合中间物种之前，互变异构，例如，在低温下，如- 1000c ，以1000c ，最好是- 100c ，以250c ，并根据无水条件下，生产乙烯胺聚合物。

Protected Monomers Silyl enamines, eg, bis(trimethylsilyl)amino-l- propene (12),保护单体含硅enamines ，例如，二（三甲基）氨基升-丙烯（ 1 2） ， enamides, eg, N-(l-isob enyl)benzamide (13), enamides ，例如， N -二（ L型isob enyl ）苯甲酰胺（ 13 ） ， vinylic carbamates, eg, N-(tert-butoxycarbonyl)-l- propenylamine (14), vinylic氨基甲酸酯类，例如， N -二（叔butoxycarbonyl ） -升- propenylamine （ 14 ） ， and enimides, eg,和enimides ，例如， N- (1-cyclohexenyl) -succinimide的N - （ 1 -环己烯基） -丁二 (15), （ 15 ） ， are regarded as "protected" monomers, since their silyl or acyl substituents help to prevent tautomerization to the imines, but can subs gently be removed under hydrolysis conditions,被视为“受保护”单体，因为他们的含硅或酰基取代有助于防止互变异构向亚胺，但潜艇可以轻轻地被删除下水解条件， eb, 电子束， in aqueous base or acid, to generate the free amine or ammonium salt, respectively.在水溶液中的基地或酸，生成的自由胺或铵盐，分别。

Other specific examples of protected monomers include 2- methyl-l-propenylacetamide, l-propenyl-tert- butylcarbamate, l-methyl-其他具体的例子，保护单体包括2 -甲基升- p ropenylacetamide，升-丙烯-叔b utylcarbamate，升-甲基 l-propenylphthalimide, N-(l-propenyl)-STABASE (16), where STABASE is L型propenylphthalimide ， N -二（升-丙烯基） - s tabase（ 1 6） ，那里是s tabase N-1,1,4,4-tetramethyldisilylazacyclopentane:的N - 1 ,1,4,4 - tetramethyldisilylazacyclopentane ： For certain applications, it is useful to retain the protecting groups on the polymer to mask the reactivity of the free amines, eg, as Lewis bases.对于某些应用，它是有用的保留保护团体对聚合物掩盖反应的自由胺，例如，作为Lewis碱。

However, the real advantage of using protected enamines is that they allow the preparation of unsubstituted poly(vinyl amine) derivatives, upon deprotection, while avoiding tautomerization.然而，真正的优势，使用保护enamines的是，他们让编写unsubstituted聚（乙烯胺）的衍生工具，后脱，同时避免互变异构。

Examples of polymers which can be obtained through polymerization of a protected monomer, followed by deprotection, include poly(l-(ethylamino)-2- methylpropene), poly(l-amino-3-phenyl-l-butene), and的例子，其中聚合物可通过聚合反应的单体保护，其次是脱，包括聚（ L - （氨基） -2 -m ethylpropene） ，聚（ L -氨基酸- 3 -苯基- L-丁烯），以及 poly(l-cyclohexylamino)-1-entene). 聚（ L - cyclohexylamino ） - 1 - entene ） 。

Enamides, enimides, and enamines differing in the protecting groups attached to nitrogen can be copolymerized. enamides ， enimides ， enamines不同，在保护团体的重视氮可以共聚。 Some protecting groups are easier to hydrolyze, or deprotect, and thus can be selectively deprotected to give partially deprotected polymers or copolymers.一些保护团体更容易水解，或deprotect ，从而可以有选择性地deprotected给予部分deprotected聚合物或共聚物。 An example is the partial deprotection of poly (vinyl trifluoroacetamide-其中一个例子是部分脱聚（乙烯基trifluoroacetamide - co-vinyl acetamide) to give poly(vinyl amine-co-vinyl acetamide) (17), where n is as defined above.合作-乙烯基乙酰胺） ，使聚（乙烯胺-合作-乙烯基乙酰胺） （ 17 ） ，其中n是如上所确定的。

Polvmerization Tertiary enamines, eg, N,N-dimethyl-N- propenylamine and 2-methyl-N-propenylpiperidine, can be copolymerized with electron-deficient monomers, including maleimide, N-ethyl maleimide, N-butyl maleimide, N-phenyl maleimide, and maleic anhydride. polvmerization大专enamines ，例如， N ， N -二氮propenylamine和2 -甲基-N - p ropenylpiperidine，可以共聚与电子缺陷单体，包括马来酰亚胺， N -乙基马来酰亚胺， N -丁基马来酰亚胺， N -苯基马来酰亚胺，和马来酸酐。 The copolymerization reactions are carried out, for example, using free radical initiators.共聚反应进行，例如，使用自由基的发起者。

Free radical initiation was effected by a diazo compound, azobisisobutyronitrile (AIBN), and a perester, tert-butylperoxybenzoate.自由基的启动是由一重氮化合物，偶氮（ aibn ） ，和perester ，叔butylperoxybenzoate 。 Other free radical initiators include water-soluble diazo compounds, such as 2,2'- azobis(amidinopropane) hydrochloride, peroxides, such as tert-butylhydroperoxide and benzoylperoxide, and dithiuram disulfides, such as tetraethylthiuram disulfide.其他自由基的发起者包括水溶性重氮化合物，例如2,2 ' -偶氮（ a midinopropane）盐酸盐，过氧化物，如叔b utylhydroperoxide和b enzoylperoxide， d ithiuram二硫化物，如t etraethylthiuram二硫键。

In general, an acceptable temperature range for the polymerization reactions is在一般，一个可接受的温度范围为聚合反应是 -100°C -100 ° C时 to 1000C, more preferably到1000c ，更最好 OOC ooc to 650C.到650c 。 Benzene, THF, toluene, water, and isopropyl alcohol have been successfully employed as solvents, although solvent is not essential.苯，四氢呋喃，甲苯，水和异丙醇已成功受聘为溶剂，虽然溶剂，是不是必需的。

Secondary and tertiary enamides, due to the beneficial electronics imparted by the protective groups, are stable precursor monomers in the production of vinyl amine derivative polymers.中学及大专enamides ，由于有利电子传授由保护团体，是稳定的前驱单体在生产乙烯胺衍生物的聚合物。 Once polymerized, the一旦聚合， precursor polymers can then be hydrolyzed to give poly(vinyl amine) derivatives.前体聚合物，然后再水解，使聚（乙烯胺）的衍生物。 The allylamide isomerization products, N-propenylformamide (NPF) and N- propenylacetamide (NPA), were polymerized using either free radical initiators, as described above, or cationic initiators.该allylamide异构化的产品， N -二propenylformamide （国家储备基金）和N - propenylacetamide （行动纲领） ，聚合使用自由基的发起者，如上文所述，或阳离子的发起者。

The cationic initiators used include a Lewis acid, tin(IV) tetrachloride, and a stabilized cation, triphenylcarbenium pentachlorostannate.阳离子发起人用于包括Lewis酸，锡（四） ，四氯化碳，和一个稳定的阳离子， triphenylcarbenium pentachlorostannate 。 Other cationic initiators include protic acids, such as perchloric acid and trifluoromethanesulfonic acid, and Lewis acids, such as boron trifluoride, aluminum trichloride, and titanium tetrachloride.其他阳离子的发起者包括protic酸，如高氯酸和trifluoromethanesulfonic酸，和Lewis酸，如三氟化硼，三氯化铝，四氯化钛。 Other initiators include iodine, diaryliodium salts, and ionizing radiation.其他发起人包括碘， diaryliodium盐，和电离辐射。

The NPF and NPA monomers were copolymerized with electron deficient monomers, such as vinyl formamide, maleimide, N-ethyl maleimide, N-butyl maleimide, N-phenyl maleimide and maleic anhydride, using, for example, free radical initiation, as described above.国家储备基金和新人民军单体共聚与电子不足的单体，如乙烯基甲酰胺，马来酰亚胺， N -乙基马来酰亚胺， N -丁基马来酰亚胺， N -苯基马来酰亚胺和马来酸酐，使用，举例来说，自由基的启动，如上文所述。 The N- propenylamide monomers should also copolymerize with vinyl acetate, acrylamide, sodium acrylate, acrylonitrile, methyl methacrylate and n-butyl acrylate, all of which have been previously copolymerized with N- vinylformamide (NVF).欧米茄propenylamide单体也应copolymerize与醋酸乙烯酯，丙烯酰胺，丙烯酸钠，丙烯腈，甲基丙烯酸甲酯和丙烯酸正丁酯，所有这些先前曾共聚与N - vinylformamide （ nvf ） 。 N-propenylamides have also been shown to copolymerize with other N-propenylamides and with NVF.的N - propenylamides也被证明是copolymerize与其他的N - propenylamides与nvf 。

The following are examples of monomer preparation and polymerizations of the invention: EXAMPLE 1 Preparation of下面举例说明单体的制备及聚合的发明：例如一的制备 1- (2-methyl-1-propenyl) -piperidine 1 -（ 2 -甲基- 1 -丙烯基） -哌啶 A reaction flask was charged with 5反应瓶被落案控以5 A 字母a molecular sieves (20g), A103 (4g), diethyl ether (40分子筛（二十〇克） ， a103 （ 4克） ，乙醚（ 40 M1), 货币供应M1 ） ， piperidine (5.12g, 8.26哌啶（五点一二克， 8月26日 mmol), mmol ） ， and a stir bar.和搅拌棒。 Isobutyraldehyde (3.60g, 49.9异丁醛（三点六零克， 49.9 mmol) mmol ） was added slowly to the mixture.加入慢慢的混合物。 The flask was then equipped with a condenser and was allowed瓶子，当时配备了冷凝器和被允许 to stir for 2 hours.挑起为2个小时。 The mixture was filtered and fractionally distilled at 800C with a pressure of 40 mmHg to give the desired enamine product, having the formula (18).混合物过滤，并略微蒸馏在800c与压力40毫米汞柱，让理想的enamine产品，具有公式（ 18 ） 。

Proton nuclear magnetic resonance (1H-NMR) was used to analyze a solution of the product in deuterated chloroform.质子核磁共振（核磁共振）是用来分析解决方案，该产品在氘氯仿。 The 1H-NMR spectrum collected on a 200 MHz instrument had a multiplet at a chemical shift of 5.3 parts per million (ppm) which integrated to one proton, a triplet at 2.5 ppm which integrated to four protons, two doublets at 1.66 ppm and 1.59 ppm which integrated to three protons each, and a multiplet from 1.4-1.2 ppm which integrated to six protons.该核磁共振谱收集在一个200 MHz的仪器有一个multiplet在化学位移5.3每100万（百万分之一）的综合，以一质子，三重在2.5 ppm的综合，以4个质子， 2 doublets在1.66 ppm和1.59 ppm的综合，以3个质子，每个和multiplet从1月4日至1月2日ppm的综合，以6个质子。

EXAMPLE 2示例2 <BR> <BR> <BR> Poly(2-methyl-1-propenylpiperidine-co-(N-ethylmaleimide)) <br> <br> <br>聚（ 2 -甲基- 1 - propenylpiperidine -合作- （的N - ethylmaleimide ） ） In a drybox, a reaction vial was charged with N-ethylmaleimide (EtMI) (0.1090 g, 0.087在一个drybox ，反应小瓶被控与N - ethylmaleimide （ etmi ） （ 0.1090克， 0.087 mmol) mmol ） and a stir bar.和搅拌棒。 A solution of 2-methyl-l-propenylpiperidine (0.55 M) and AIBN (0.004 M) in benzene was prepared, as described in Example 1.解决办法2 -甲基-升- propenylpiperidine （ 0.55米）和aibn （ 0.004米）在苯的准备，正如所描述的范例1 。 The 2-methyl-1- propenylpiperidine and AIBN solution (1.55 mL, 0.085 and 6.2 x 10-3 2 -甲基- 1 - propenylpiperidine和aibn解决方案（ 1.55毫升， 0.085和6.2 x 10月3日 mmol) mmol ） was then added to the vial containing EtMI.当时添加到小瓶含有etmi 。 Upon mixing the solution became light yellow in color.混合后的解决办法，成为浅黄色的颜色。 The vial was capped, sealed with TEFLONS tape, and quickly brought out of the drybox and placed in the photolysis chamber.该小瓶被限制，密封与teflons磁带，并迅速带出的drybox并放置在光厅举行会议。 During photolysis at 366 nm, the polymer precipitated from solution.在光在366 nm时，聚合物沉淀，从解决方案。 The polymer was聚合物 isolated by precipitation into diethyl ether and dried in vacuo, and had the formula (19).分离沉淀到乙醚和干果在真空中，并已公式（ 19 ） 。 In all examples, n is as defined above.在所有的例子， N是如上所确定的。

Thermolysis of the AIBN initiator was also effective for the copolymerization of the enamides.热的aibn的发起者，也是有效的为共聚的enamides 。 The procedure used was the same as above except that the reaction mixture was sealed in an ampule under vacuum and placed in an oil bath at 1000C using maleic anhydride and EtMI as comonomers.所采用的程序是一样的，除了上述反应混合物被密封在一安瓿真空条件下并放置在一油浴在1000c使用顺丁烯二酸酐和etmi作为comonomers 。

EXAMPLE 3 Preparation of N,N-dimethylamino-l-propene A reaction tube例如3制备N ， N -二甲氨基-升-丙烯反应管 was 是 charged with N,N- dimethylallylamine (0.5013g, 5.90被控以N ， N -二dimethylallylamine （ 0.5013克， 5.90 mmol) mmol ） and RuClH(PPh3)3 (0.032g, 0.091和ruclh （ pph3 ） 3 （ 0.032克， 0.091 mmol). mmol ） 。 The reaction tube was heated to 600C overnight.反应管加热到600c通宵。 The isomerized monomer having the formula (20) was isolated from the catalyst by vacuum distillation.该异构化单体有公式（ 20 ）被分离出的催化剂真空蒸馏。

Proton nuclear magnetic resonance (1H-NMR) was used to analyze a solution of the product in deuterated chloroform.质子核磁共振（核磁共振）是用来分析解决方案，该产品在氘氯仿。 The 1H-NMR spectrum collected on a 200 MHz instrument had a doublet at a chemical shift of 5.88 parts per million (ppm) which integrated to one proton, a multiplet at 4.19 ppm which integrated to one proton, a singlet at 2.5 ppm which integrated to six protons, a doublet at 1.60 ppm which integrated to three protons, and a broad peak at 0.8 ppm which integrated to two protons.该核磁共振谱收集在一个200 MHz的仪器有一个双线在化学位移5.88百万分之（百万分之一）的综合，以一质子， 1 multiplet在4.19 ppm的综合，以一质子，单在2.5 ppm的综合到6个质子， 1双在1.60 ppm的综合三个质子，和广阔的高峰期， 0.8 ppm的综合两个质子。

EXAMPLE 4例如4 <BR> <BR> <BR> PolyeN,N-dimethylamino-1-propene-co-(N-ethylmaleimide)) <br> <br> <br> polyen ， N -二甲氨基- 1 -丙烯-合作- （的N - ethylmaleimide ） ） In a drybox, a vial was charged with N,N- dimethylamino-l-propene (0.0850 g, 1.00在一个drybox ，一小瓶被落案控以N ， N -二二甲升-丙烯（ 0 .0850克， 1 .00 mmol), mmol ） ， EtMI (0.1250 g, 1.00 etmi （ 0.1250克， 1.00 mmol), mmol ） ， and a stir bar.和搅拌棒。 A solution of AIBN (0.500 mL, 0.032 M, 5.11 x 10-4解决aibn （ 0.500毫升， 0.032米， 5.11 x 10月4日 mmol) mmol ） in benzene was then added to the vial containing the monomers.在苯，当时添加到小瓶含有单体。 The vial was capped, sealed with TEFLONS tape, and quickly brought out of the drybox and placed in the photolysis chamber.该小瓶被限制，密封与teflons磁带，并迅速带出的drybox并放置在光厅举行会议。

During photolysis at 366 nm, the polymer precipitated from solution.在光在366 nm时，聚合物沉淀，从解决方案。 The polymer was isolated by precipitation into diethyl ether and聚合物分离沉淀到乙醚和 dried 冻干 in vacuo, and had the formula (21).在真空中，并已公式（ 21 ） 。

EXAMPLE 5 Preparation of 1-Propenylformamide In a drybox, a Schlenk flask was charged with N- allylformamide (0.9989 g,11.8例如5制备1 - propenylformamide在一个drybox ， schlenk瓶被控与N - allylformamide （ 0.9989克， 8月11日 mmol), mmol ） ， RuClH(PPh3)3 (0.0495 g, 0.0496 ruclh （ pph3 ） 3 （ 0.0495克， 0.0496 mmol), mmol ） ， toluene (5 mL), and a stir bar.甲苯（ 5毫升） ，和一个搅拌棒。 The flask was taken from the box, fitted with a condenser, and heated to reflux for several hours under an argon atmosphere.瓶子是采取从盒子，带有冷凝器，并加热至回流几个小时，下氩气氛中进行的。 The solvent was then removed under reduced pressure to give a yellow oil.溶剂，当时删除的压力下，减少给一个黄色的油。 The oil was distilled using a Kugelrohr apparatus under partial vacuum to give an 87% yield of isomerized product with a cis:trans ratio of 0.46:0.54, having the formula (22).石油是蒸馏使用kugelrohr仪器下局部真空，使一87 ％ ，产量的异构化产品与独联体：跨的比例0.46:0.54 ，有公式（ 22 ） 。

Proton nuclear magnetic resonance (1H-NMR) was used to analyze a solution of the product in deuterated chloroform.质子核磁共振（核磁共振）是用来分析解决方案，该产品在氘氯仿。 The 1H-NMR spectrum collected on a 200 MHz instrument had a broad peak at a chemical shift of 8.5 parts per million (ppm) which integrated to one proton and four multiplets at 8.0 ppm, 6.7-6.2 ppm, 5.3-4.8 ppm, and 1.6 ppm which integrated to one proton each.该核磁共振谱收集在一个200 MHz的文书进行了广泛的高峰期在化学位移8.5每100万（百万分之一）的综合，以一质子和4 multiplets在8.0 ppm的，六月七日至六月二日百万分之一， 5月3日至4月8日ppm ，使用和1.6 ppm的综合，以一质子每个。

EXAMPLE 6例如六 Poly (1-propenylacetamide) 聚（ 1 - propenylacetamide ） l-Propenylacetamide was prepared by the method of Stille and Becker (J. L型propenylacetamide编写方法stille和贝克尔（ j. Org. 组织。 Chem.化学。 1980, 45, 2139-2145), by ref fluxing N-allylacetamide with HRuCl(PPh3)3 in benzene under argon for 40 hours. 1980年， 45岁， 2139年至2145年） ，由参熔合的N - allylacetamide与hrucl （ pph3 ） 3 ，在苯下，氩气为40小时。 The l-propenylacetamide was isolated by distillation. L型propenylacetamide分离蒸馏。

In a drybox, an ampule was charged with 1- propenylacetamide (0.2103 g, 2.15在一个drybox ， 1安瓿被落案控以1 -p ropenylacetamide（ 0 .2103克， 2月1 5日 mmol) mmol ） and a stir bar.和搅拌棒。

The ampule was removed from the drybox and tert-butyl该安瓿被拆掉，从drybox和叔丁基 peroxybenzoate (0.0073 g, 0.038 peroxybenzoate （ 0.0073克， 0.038 mmol) mmol ） was added under an argon atmosphere using Schlenk techniques.加入下一个氩气使用schlenk技术。 The ampule was then degassed, sealed under vacuum and placed in a 1500C oil bath.该安瓿当时脱气，密封真空条件下，并放置在一个1500c油浴。 After several hours the ampule contents were dissolved in DMF, precipitated into acetone and dried in vacuo.经过几个小时的安瓿内容被解散在DMF ，沉淀成丙酮和干果在真空中。

In a drybox, a reaction flask was charged with 1- propenylacetamide (0.2505 g, 2.56 mmol), benzene (0.5 mL) and a stir bar.在一个drybox ，反应瓶被落案控以1 -p ropenylacetamide（ 0 .2505克， 2 .56m mol） ，苯（ 0 .5毫升）和搅拌棒。 The flask was then sealed with a septa and removed from the drybox.瓶子是密封，然后与一隔，并取消从drybox 。 A solution of ZnCl2 (25解决氯化锌（ 25 pL,1.0 特等， 1.0 M, 0.025男， 0.025 mmol) mmol ） in 1,2-dichloroethane was added to the flask via syringe.在1,2 -二氯乙烷被添加到烧瓶通过注射器。 After several hours at room temperature the contents became very viscous.后几个小时，在室温下的内容，成为粘性非常大。 The contents were then dissolved in DMF, precipitated into acetone, and dried in vacuo,, having the formula (23).内容，然后溶解于二甲基甲酰胺，沉淀成丙酮，和干果在真空中， ，有公式（ 23 ） 。

An alternative procedure was also used.另一种程序，还采用了。 In a drybox, a reaction vial was charged with 1- propenylacetamide (0.2018 g, 2.06在一个drybox ，反应小瓶被落案控以1 -p ropenylacetamide（ 0 .2018克， 2 .06 mmol), mmol ） ， triphenylcarbenium pentachlorostannate (0.001 g, 0.002 triphenylcarbenium pentachlorostannate （ 0.001克， 0.002 mmol), mmol ） ， benzene (0.75 mL) and a stir bar.苯（ 0.75毫升）和搅拌棒。 The mixture was allowed to stir in the drybox for several days.混合物被允许轰动，在drybox数天。 The vial contents were dried in vacua.该小瓶的内容，干燥，在vacua 。

EXAMPLE 7例如7 Poly(l-propenylacetamide-co-maleimide) 聚（ L - propenylacetamide -合作-酰亚胺） In a drybox, a reaction vial was charged with maleimide (0.0969 g, 1.00在一个drybox ，反应小瓶被落案控以马来酰亚胺（ 0.0969克， 1.00 mmol), mmol ） ， 1-propenylacetamide (0.1019 g, 1.04 1 - propenylacetamide （ 0.1019克， 1.04 mmol) mmol ） and a stir bar.和搅拌棒。 A solution of AIBN解决aibn (0.01 M) in benzene was prepared. （ 0.01 m ）在苯的准备。 The AIBN solution (0.50 Ml, 5.0 x该aibn解决方案（ 0.50毫升， 5.0 x 10-4 10月4日 mmol) mmol ） was then added to the vial containing the monomers.当时添加到小瓶含有单体。 The vial was capped, sealed with TEFLONS tape, and quickly brought out of the drybox and placed in the photolysis chamber.该小瓶被限制，密封与teflons磁带，并迅速带出的drybox并放置在光厅举行会议。 During photolysis at 366 nm, the polymer precipitated from solution.在光在366 nm时，聚合物沉淀，从解决方案。 The polymer was isolated by precipitation into diethyl ether and dried in vacuo, and had the formula (24).聚合物分离沉淀到乙醚和干果在真空中，并已公式（ 24 ） 。

Additionally, thermolysis of the initiator was also effective for the copolymerization of the enamides.此外，热的发起者，也是有效的为共聚的enamides 。

The procedure used was the same as above except that the reaction mixture was sealed in an ampule under vacuum and placed in an oil bath at 650C.所采用的程序是一样的，除了上述反应混合物被密封在一安瓿真空条件下并放置在一油浴在650c 。

EXAMPLE 8例如8 PolyX1-propenylacetamide-co-(N-vinylformamide)) polyx1 - propenylacetamide -合作- （的N - vinylformamide ） ） In a drybox, a reaction vial was charged with 1- propenylacetamide (0.0998 g, 1.01在一个drybox ，反应小瓶被落案控以1 -p ropenylacetamide（ 0 .0998克， 1 .01 mmol), mmol ） ， N-vinylformamide (0.1018 g, 1.43的N - vinylformamide （ 0.1018克， 1.43 mmol), mmol ） ， triphenylcarbenium pentachlorostannate (0.001 g, 0.002 triphenylcarbenium pentachlorostannate （ 0.001克， 0.002 mmol), mmol ） ， and a stir和轰动 bar.大律师公会。 The vial contents were stirred and solidified overnight, to give polymer (25).该小瓶的内容分别为搅拌和凝固在一夜之间，让聚合物（ 25 ） 。

Uses and Properties of the New用途和性能的新 Homoolvmers homoolvmers and和 Copolymers 共聚物 The homopolymers and copolymers of the invention have commercial utility including, but not limited to the known applications of vinyl amide and vinyl amine homopolymers and copolymers.该均聚物和共聚物的发明具有商业实用工具，包括但不限于已知的应用乙烯酰胺和乙烯胺均聚物和共聚物。 For example, these polymers have applications in the textile, adhesives and coatings, paper, petroleum, water treatment, cosmetic, and pharmaceutical industries.举例来说，这些聚合物的应用在纺织，粘合剂和涂料，造纸，石油，水处理，化妆品，工业和制药工业。 These polymers have broader application than the parent poly(vinyl amine), because the novel alkyl side chains attached at alternate positions on the polymer backbone provide an added diversity element to the new polymers, which allows the properties of the polymer, eg, solubility, to be specifically tailored for a desired use.这些聚合物有更广泛的应用，比父母聚（乙烯胺） ，因为小说烷基侧链附于候补的立场聚合物的骨干提供了一个补充，多样性的组成部分，以新的聚合物，这使得性能的聚合物，例如，溶解度，要专门为一理想的使用。

For example, an n-butyl group attached at every other position of the polymer backbone would increase solubility in non-polar solvents, eg, hydrocarbons.举例来说，一个正丁酯集团十分重视在每一个其他的立场，聚合物的骨干，将增加的溶解度在非极性溶剂中，例如，碳氢化合物。 A substituted aryl, eg, 4-phenol, attached at every other取代芳基，例如， 4 -苯酚，重视每一个其他 position of the polymer backbone would increase the solubility in polar organic solvents, eg, ethyl acetate.的立场，聚合物的骨干，将增加的溶解度在极性有机溶剂，如乙酸乙酯。

Specific applications of the polymers of this invention can include flocculence enhancement in the paper manufacturing and water treatment, and maintenance of high viscosity for petroleum products, to facilitate pumping.具体应用聚合物本发明的，可以包括flocculence加强在文件中制造业和水处理，及维修高粘度石油产品，以方便抽水。 The polymers can also be used to prepare ion- exchange membranes.聚合物也可以被用来编写离子交换膜。

Other Embodiments It is to be understood that while the invention has been described in conjunction with the detailed description thereof, that the foregoing description is intended to illustrate and not limit the scope of the appended claims.其他的体现，这是可以理解的同时，该发明已被描述在与详细的说明，即前述说明的用意是说明，而不是限制的范围所附的索赔。 Other aspects, advantages, and modifications are within the scope of the following claims.其他方面的优势，和修改都在范围下列索赔。