聚（乙烯胺）類似物的聲明，以 Federal lav 聯邦低 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.贊助的研究發明，這是與政府的支持下，授權號碼，移民和難民事務部- 9350473和授權號碼，移民和難民事務部- 9634528頒發的國家科學基金會。 The Government has certain rights in the invention.政府的某些權利的發明。
基本介紹
- 中文名：聚（乙烯胺）
- CAS：CAS#: 49553-92-6
發明背景和過程,單體的製備及聚合的發明例子,
發明背景和過程
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的發明，這項發明涉及到的形成，乙烯胺衍生物及其聚合形成新的聚（乙烯胺）類似物。
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）及其類似物的成員，一個重要的類陽離子聚電解質，這是非常可取的材料套用在紡織，粘合劑和塗料，造紙，石油，水處理，化妝品，工業和製藥工業。
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）類似物不能獲得通過聚合明顯的母公司分子，乙烯胺，因為乙烯胺是不穩定與尊重其亞胺互變異構體， 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）類似物，因此已獲得的間接方法，例如，釷Hofmann重排聚（丙烯醯胺） ，或施密特反應的聚（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.該發明的發明是基於發現新的聚（乙烯胺）類似物，可以編寫的聚合體獲得的異構化反應的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體的組合與其他聚合基板。 These new polymers and copolymers are polyelectrolytes, bearing side chains which become positively charged at low pH.這些新的聚合物和共聚物是聚電解質，同時側鏈成為帶正電荷，在低pH值。 Furthermore, the new此外，新 methods require fewer steps than methods previously employed to obtain poly(vinyl amines).方法需要較少的步驟，方法比以前受聘取得聚（乙烯胺） 。
In general, the invention features a polymer在一般的發明，功能高分子 having the formula (1):有公式（ 1 ） ： where R1 through R4, independently, are hydrogen; an alkyl, eg, R1的情況下，通過R4的，獨立的，是氫氣;一烷基，例如， CaH2a+lt cah2a +審裁處 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 ;一醯基，例如， coh ， coch3 ，或cocf3 ;或一鹵素，例如，男，的C1 ，溴，或者我; R5的和r6 ，獨立可氫氣;烷基;芳;醯基; alkoxycarbonyl ，例如， cooch3 ， cooc （甲基） 3 ，或cooch2ch3 ;或含矽，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最多可以有一萬，十萬，百萬，或更高。
In some cases, R1, R2, R3, and R4 are all hydrogen to give a polymer having formula (2).在某些情況下， R1的， R2的， R3的，和R4都是氫氣，使聚合物後，公式（ 2 ） 。
R5 also can be hydrogen, and R6 can be an acyl, forming a poly(crotyl amide). R5的也可以氫， r6可以是一個醯基，形成了聚（ crotyl醯胺） 。 Some specific examples include poly(crotyl formamide), poly(crotyl acetamide), poly (crotyl dichloroacetamide), poly (crotyl一些具體的例子包括聚（ crotyl甲醯胺） ，聚（ crotyl乙醯胺） ，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都可以醯基，形成了聚（ crotyl醯亞胺） 。 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可以附在對方，以形成一個環形結構，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.另一個方面的發明，是一個法製備聚合物獲取，然後服從，以聚合條件， vinylic單體後，公式（ 4 ） ，其中R1的，以r6是如上所確定的。
The monomer can be prepared by isomerization of the allylic species with the formula (5).單體可以編寫的異構化反應的烯丙基物種與公式（ 5 ） 。
Polymerization methods include, but are not limited to, those described in the detailed description.聚合方法包括，但不僅限於，這些描述的詳細描述。
In another aspect, the invention features a copolymer having the formula (6):在另一個方面，該發明具有共聚物具有公式（ 6 ） ： wherein the repeating units (7) and (8) can be linked in any其中重複單位（ 7 ） （ 8 ）可以掛在任何 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.為了和在任何方向，例如，單位（ 7 ）可以反覆多次在共聚物鏈的前一個單位， （ 8 ）發生，反之亦然。 R1 to R6 are defined as above; R7 and R1的，以r6被界定為以上; r7和 Rg, 的RG ， independently, are hydrogen, alkyl, aryl, acyl, or halogen.獨立，是氫，烷基，芳基，醯基，或鹵素。 R8 and r8和 R10, 奧迪R10 V型12 ， independently, are hydrogen, alkyl, aryl, acyl,獨立，是氫，烷基，芳基，醯基， 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 ;而設計，和r12 ，獨立，是氫，烷基，芳基，醯基，或含矽。
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最多可以有一萬，十萬，百萬，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 ;何處r13可以氫，烷基，芳基，含矽，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.是氫氣。
In another aspect, the invention features a method for preparing a copolymer from monomers having the formulae (10) and (11), where R1 to在另一個方面，發明特點的方法，準備從單體的共聚物具有公式（ 10 ）及（ 11 ） ，其中R1的要 Rlo rlo are as defined above, by subjecting these monomers to polymerization conditions.是如上所確定的，受到這些單體以聚合條件。
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.單體（ 11 ）可以，例如，順丁烯二酸酐;醯亞胺;一N -烷基醯亞胺，例如， N -丁基馬來醯亞胺; N -芳基醯亞胺，例如， N -二xylyl醯亞胺;的N -含矽醯亞胺，例如， n -三甲基矽醯亞胺;或一N -醯基醯亞胺，例如， N -二pivaloyl馬來。
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，單體（ 11 ）可以，例如， vinylic胺，一vinylic酯， vinylic醯胺，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，所有的技術和科學術語，此處使用的具有相同的含義，作為普遍的理解，一個普通的技能，在藝術，這是屬於發明。 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.雖然方法和材料，類似或相等於那些此處所述，可用於在實踐中或測試本發明，首選的方法和材料，敘述如下。 All publications, patent applications, patents, and other references mentioned herein are incorporated by reference in their entirety.所有出版物，專利申請，專利和其他參考此處提及的是通過提及而納入他們的全部內容。 In case of conflict, the present application, including definitions, will control.在衝突的情況下，目前的套用，包括定義，將控制。 In addition, the materials, methods, and examples are illustrative此外，該材料，方法和例子是說明性 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，利用這種新方法是利用方便烯胺衍生物作為單體的前體。 Allylic amine derivatives are inexpensive to prepare and are very stable.烯胺衍生物是廉價的準備，而且非常穩定。 The facile isomerization described herein provides the reactive vinyl amine derivatives necessary for polymerization.該簡易異構化此處所述的規定，無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.聚合物的發明是獨一無二的，因為它們不僅包括胺的功能附加在每一個其他的碳原子沿聚合物的骨幹，賦予polyelectrolytic性能，而且還一烷基或烷基衍生的重視中間碳原子的骨幹。 In the parent poly(vinyl amine),在家長聚（乙烯胺） ， this position is simply occupied by a hydrogen atom.這一立場是簡單地被占領的一個氫原子。
This allows for tremendous diversity in the realm of poly(vinyl amine) derivatives.這使得巨大的多樣性的境界聚（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，親脂性組在這個軌跡可以用來建立相轉移催化劑，甚至烴類可溶性聚電解質。
Other features and advantages of the invention will be apparent from the following detailed description, and from the claims.其他的特點和優勢的發明，將明顯從下面的詳細描述，並從索賠。
Detailed Description The isomerization and subsequent polymerization of allylamines, allylamides, and allylimides yields new polymers belonging to the family of poly(vinyl amine) analogs.詳細描述異構化和隨後的聚合allylamines ， allylamides ， allylimides產量新的聚合物，屬於家庭的聚（乙烯胺）類似物。 By combining the intermediate isomerization products with other polymerizable molecules, new copolymers are also obtained.相結合的中間異構化的產品與其他聚合分子，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.由於側鏈對聚合物承擔氮原子與一取消共用電子對，聚合物成為質子在酸性溶液中產生polycationic物種。 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.新方法允許範圍廣泛的聚（乙烯胺）類似物，以獲得在幾個步驟，作為烯前體是現成的。
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.單體三類基板可以用來形成穩定的或短暫的乙烯胺類似物後，異構化： 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.這些基板催化isomerizable ，以enamines ， enamides ， enimides ，分別是，所有這一切都是在結構上類似要么乙烯胺或受保護的乙烯胺單體。
In the following description, primary enamines, alkyl enamines, and aryl enamines are called unprotected monomers.在下面的說明，主要enamines ，烷基enamines ，和芳enamines是所謂的未受保護的單體。 Enamides (acyl enamines), enimides (diacyl enamides （醯基enamines ） ， enimides （二醯基 enamines), vinylic carbamates (alkoxycarbonyl enamines), and silyl enamines are protected monomers. enamines ） ， vinylic氨基甲酸酯（ alkoxycarbonyl enamines ） ，含矽enamines保護單體。
Unprotected Monomers Enamines offer the most direct approach to the preparation of vinyl amine-derived copolymers.未受保護的單體enamines提供最直接的方法來製備乙烯胺衍生共聚物。 The polymerization of these compounds incorporates an amine functionality into the polymer without the need for deprotection of a precursor.聚合這些化合物包含一胺的功能，到聚合物，而不需要脫一個前兆。 Depending on the amine substitution, however, an enamine can be unstable with respect to its imine form.根據對胺替代，不過，一enamine可以不穩定與尊重其亞胺形式。 Generally, less substituted enamines, eg, primary enamines, are less stable than their more substituted relatives.一般來說，少取代enamines ，例如，國小enamines ，較差的穩定比他們更取代的親屬。 Hence, less substituted monomers are most amenable to copolymerization.因此，少取代單體是最適合共聚。
Secondary and tertiary enamines have alkyl or aryl substituents, eg, ethyl, isobutyl, phenyl or substituted phenyls.中學及大專enamines有烷基或芳基取代，例如，乙基，異丁基，苯基或取代phenyls 。 These substituents help to stabilize the monomers with respect to the unsubstituted vinyl amines.這些取代基有助於穩定單體方面向unsubstituted乙烯胺。
A number of routes lead to tertiary enamines, including isomerization.一些路線導致高等教育enamines ，包括異構化。 For example, many tertiary allylamines isomerize to例如，許多大專allylamines isomerize ，以 tertiary 大專 enamines using a catalyst. enamines使用的催化劑。 Examples of例子 isomerization 異構化 catalysts include those derived from ruthenium, eg, 10 mol%催化劑包括那些來自釕，例如， 10 mol %時 RuClH(CO) (PPh3) ruclh （合作） （ pph3 ） in ref fluxing benzene for 1 to 15 hours; cobalt, eg, 1 mol% CoH(N2)(PPh3) in在參熔合苯為1至15小時;鈷，例如， 1 mol %時coh （氮氣） （ pph3 ）在 tetrahydrofuran 四氫呋喃 (THF) at 800C for 15 hours; rhodium, eg, 1 mol% （四氫呋喃）在800c為15小時;銠，例如， 1 mol %時 [Rh(diphosphine)(THF)n]+~Cl04 [銠（膦） （四氫呋喃） N的] + 〜 cl04 in THF at 400C for 23 hours, the diphosphine ligand can be 2,2'-在THF在400c為23小時，雙膦配體可以2,2 ' - bis(diphenylphosphino)-l,l'-binaphthyl 雙（二苯膦基） -升的L' -聯萘 (BINAP); or molybdenum, eg, 1 mol% trans-Mo(N2)(Ph2PCH2CH2PPH2)2 in toluene at 1000C for 1.5 to 5 hours. （ binap ） ;或鉬，例如， 1 mol %與跨鉬（氮氣） （ ph2pch2ch2pph2 2 ）在甲苯在1000c為1.5至5小時。
Alternatively, the isomerization can be catalyzed by base.此外，異構化，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.包括鉀叔butoxide或鉀醯胺對氧化鋁。
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.中學enamines較差的穩定比大專enamines ，且往往tautomerize到相應的亞胺，雖然異構化中學allylamines與釕催化劑允許有選擇性的，短暫的形成，中學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.對於這些化合物，這是必要的聚合中間物種之前，互變異構，例如，在低溫下，如- 1000c ，以1000c ，最好是- 100c ，以250c ，並根據無水條件下，生產乙烯胺聚合物。
Protected Monomers Silyl enamines, eg, bis(trimethylsilyl)amino-l- propene (12),保護單體含矽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 ）苯甲醯胺（ 13 ） ， vinylic carbamates, eg, N-(tert-butoxycarbonyl)-l- propenylamine (14), vinylic氨基甲酸酯類，例如， N -二（叔butoxycarbonyl ） -升- propenylamine （ 14 ） ， and enimides, eg,和enimides ，例如， N- (1-cyclohexenyl) -succinimide的N - （ 1 -環己烯基） -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,被視為“受保護”單體，因為他們的含矽或醯基取代有助於防止互變異構向亞胺，但潛艇可以輕輕地被刪除下水解條件， eb, 電子束， in aqueous base or acid, to generate the free amine or ammonium salt, respectively.在水溶液中的基地或酸，生成的自由胺或銨鹽，分別。
Other specific examples of protected monomers include 2- methyl-l-propenylacetamide, l-propenyl-tert- butylcarbamate, l-methyl-其他具體的例子，保護單體包括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） ，那裡是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.對於某些套用，它是有用的保留保護團體對聚合物掩蓋反應的自由胺，例如，作為Lewis鹼。
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，真正的優勢，使用保護enamines的是，他們讓編寫unsubstituted聚（乙烯胺）的衍生工具，後脫，同時避免互變異構。
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，其中聚合物可通過聚合反應的單體保護，其次是脫，包括聚（ L - （氨基） -2 -m ethylpropene） ，聚（ L -胺基酸- 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，在保護團體的重視氮可以共聚。 Some protecting groups are easier to hydrolyze, or deprotect, and thus can be selectively deprotected to give partially deprotected polymers or copolymers.一些保護團體更容易水解，或deprotect ，從而可以有選擇性地deprotected給予部分deprotected聚合物或共聚物。 An example is the partial deprotection of poly (vinyl trifluoroacetamide-其中一個例子是部分脫聚（乙烯基trifluoroacetamide - co-vinyl acetamide) to give poly(vinyl amine-co-vinyl acetamide) (17), where n is as defined above.合作-乙烯基乙醯胺） ，使聚（乙烯胺-合作-乙烯基乙醯胺） （ 17 ） ，其中n是如上所確定的。
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大專enamines ，例如， N ， N -二氮propenylamine和2 -甲基-N - p ropenylpiperidine，可以共聚與電子缺陷單體，包括馬來醯亞胺， N -乙基馬來醯亞胺， N -丁基馬來醯亞胺， N -苯基馬來醯亞胺，和馬來酸酐。 The copolymerization reactions are carried out, for example, using free radical initiators.共聚反應進行，例如，使用自由基的發起者。
Free radical initiation was effected by a diazo compound, azobisisobutyronitrile (AIBN), and a perester, tert-butylperoxybenzoate.自由基的啟動是由一重氮化合物，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.其他自由基的發起者包括水溶性重氮化合物，例如2,2 ' -偶氮（ a midinopropane）鹽酸鹽，過氧化物，如叔b utylhydroperoxide和b enzoylperoxide， d ithiuram二硫化物，如t etraethylthiuram二硫鍵。
In general, an acceptable temperature range for the polymerization reactions is在一般，一個可接受的溫度範圍為聚合反應是 -100°C -100 ° C時 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，四氫呋喃，甲苯，水和異丙醇已成功受聘為溶劑，雖然溶劑，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.中學及大專enamides ，由於有利電子傳授由保護團體，是穩定的前驅單體在生產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.前體聚合物，然後再水解，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.該allylamide異構化的產品， N -二propenylformamide （國家儲備基金）和N - propenylacetamide （行動綱領） ，聚合使用自由基的發起者，如上文所述，或陽離子的發起者。
The cationic initiators used include a Lewis acid, tin(IV) tetrachloride, and a stabilized cation, triphenylcarbenium pentachlorostannate.陽離子發起人用於包括Lewis酸，錫（四） ，四氯化碳，和一個穩定的陽離子， 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.其他陽離子的發起者包括protic酸，如高氯酸和trifluoromethanesulfonic酸，和Lewis酸，如三氟化硼，三氯化鋁，四氯化鈦。 Other initiators include iodine, diaryliodium salts, and ionizing radiation.其他發起人包括碘， diaryliodium鹽，和電離輻射。
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.國家儲備基金和新人民軍單體共聚與電子不足的單體，如乙烯基甲醯胺，馬來醯亞胺， N -乙基馬來醯亞胺， N -丁基馬來醯亞胺， N -苯基馬來醯亞胺和馬來酸酐，使用，舉例來說，自由基的啟動，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).歐米茄propenylamide單體也應copolymerize與醋酸乙烯酯，丙烯醯胺，丙烯酸鈉，丙烯腈，甲基丙烯酸甲酯和丙烯酸正丁酯，所有這些先前曾共聚與N - vinylformamide （ nvf ） 。 N-propenylamides have also been shown to copolymerize with other N-propenylamides and with NVF.的N - propenylamides也被證明是copolymerize與其他的N - propenylamides與nvf 。
單體的製備及聚合的發明例子
The following are examples of monomer preparation and polymerizations of the invention: EXAMPLE 1 Preparation of下面舉例說明單體的製備及聚合的發明：例如一的製備 1- (2-methyl-1-propenyl) -piperidine 1 -（ 2 -甲基- 1 -丙烯基） -哌啶 A reaction flask was charged with 5反應瓶被落案控以5 A 字母a molecular sieves (20g), A103 (4g), diethyl ether (40分子篩（二十〇克） ， a103 （ 4克） ，乙醚（ 40 M1), 貨幣供應M1 ） ， piperidine (5.12g, 8.26哌啶（五點一二克， 8月26日 mmol), mmol ） ， and a stir bar.和攪拌棒。 Isobutyraldehyde (3.60g, 49.9異丁醛（三點六零克， 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，當時配備了冷凝器和被允許 to stir for 2 hours.挑起為2個小時。 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).混合物過濾，並略微蒸餾在800c與壓力40毫米汞柱，讓理想的enamine產品，具有公式（ 18 ） 。
Proton nuclear magnetic resonance (1H-NMR) was used to analyze a solution of the product in deuterated chloroform.質子核磁共振（核磁共振）是用來分析解決方案，該產品在氘氯仿。 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.該核磁共振譜收集在一個200 MHz的儀器有一個multiplet在化學位移5.3每100萬（百萬分之一）的綜合，以一質子，三重在2.5 ppm的綜合，以4個質子， 2 doublets在1.66 ppm和1.59 ppm的綜合，以3個質子，每個和multiplet從1月4日至1月2日ppm的綜合，以6個質子。
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在一個drybox ，反應小瓶被控與N - ethylmaleimide （ etmi ） （ 0.1090克， 0.087 mmol) mmol ） and a stir bar.和攪拌棒。 A solution of 2-methyl-l-propenylpiperidine (0.55 M) and AIBN (0.004 M) in benzene was prepared, as described in Example 1.解決辦法2 -甲基-升- propenylpiperidine （ 0.55米）和aibn （ 0.004米）在苯的準備，正如所描述的範例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解決方案（ 1.55毫升， 0.085和6.2 x 10月3日 mmol) mmol ） was then added to the vial containing EtMI.當時添加到小瓶含有etmi 。 Upon mixing the solution became light yellow in color.混合後的解決辦法，成為淺黃色的顏色。 The vial was capped, sealed with TEFLONS tape, and quickly brought out of the drybox and placed in the photolysis chamber.該小瓶被限制，密封與teflons磁帶，並迅速帶出的drybox並放置在光廳舉行會議。 During photolysis at 366 nm, the polymer precipitated from solution.在光在366 nm時，聚合物沉澱，從解決方案。 The polymer was聚合物 isolated by precipitation into diethyl ether and dried in vacuo, and had the formula (19).分離沉澱到乙醚和乾果在真空中，並已公式（ 19 ） 。 In all examples, n is as defined above.在所有的例子， N是如上所確定的。
Thermolysis of the AIBN initiator was also effective for the copolymerization of the enamides.熱的aibn的發起者，也是有效的為共聚的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.所採用的程式是一樣的，除了上述反應混合物被密封在一安瓿真空條件下並放置在一油浴在1000c使用順丁烯二酸酐和etmi作為comonomers 。
EXAMPLE 3 Preparation of N,N-dimethylamino-l-propene A reaction tube例如3製備N ， N -二甲氨基-升-丙烯反應管 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.反應管加熱到600c通宵。 The isomerized monomer having the formula (20) was isolated from the catalyst by vacuum distillation.該異構化單體有公式（ 20 ）被分離出的催化劑真空蒸餾。
Proton nuclear magnetic resonance (1H-NMR) was used to analyze a solution of the product in deuterated chloroform.質子核磁共振（核磁共振）是用來分析解決方案，該產品在氘氯仿。 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.該核磁共振譜收集在一個200 MHz的儀器有一個雙線在化學位移5.88百萬分之（百萬分之一）的綜合，以一質子， 1 multiplet在4.19 ppm的綜合，以一質子，單在2.5 ppm的綜合到6個質子， 1雙在1.60 ppm的綜合三個質子，和廣闊的高峰期， 0.8 ppm的綜合兩個質子。
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在一個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.和攪拌棒。 A solution of AIBN (0.500 mL, 0.032 M, 5.11 x 10-4解決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，當時添加到小瓶含有單體。 The vial was capped, sealed with TEFLONS tape, and quickly brought out of the drybox and placed in the photolysis chamber.該小瓶被限制，密封與teflons磁帶，並迅速帶出的drybox並放置在光廳舉行會議。
During photolysis at 366 nm, the polymer precipitated from solution.在光在366 nm時，聚合物沉澱，從解決方案。 The polymer was isolated by precipitation into diethyl ether and聚合物分離沉澱到乙醚和 dried 凍乾 in vacuo, and had the formula (21).在真空中，並已公式（ 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製備1 - propenylformamide在一個drybox ， schlenk瓶被控與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） ，和一個攪拌棒。 The flask was taken from the box, fitted with a condenser, and heated to reflux for several hours under an argon atmosphere.瓶子是採取從盒子，帶有冷凝器，並加熱至回流幾個小時，下氬氣氛中進行的。 The solvent was then removed under reduced pressure to give a yellow oil.溶劑，當時刪除的壓力下，減少給一個黃色的油。 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).石油是蒸餾使用kugelrohr儀器下局部真空，使一87 % ，產量的異構化產品與獨立國協：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.質子核磁共振（核磁共振）是用來分析解決方案，該產品在氘氯仿。 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.該核磁共振譜收集在一個200 MHz的文書進行了廣泛的高峰期在化學位移8.5每100萬（百萬分之一）的綜合，以一質子和4 multiplets在8.0 ppm的，六月七日至六月二日百萬分之一， 5月3日至4月8日ppm ，使用和1.6 ppm的綜合，以一質子每個。
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編寫方法stille和貝克爾（ j. Org. 組織。 Chem.化學。 1980, 45, 2139-2145), by ref fluxing N-allylacetamide with HRuCl(PPh3)3 in benzene under argon for 40 hours. 1980年， 45歲， 2139年至2145年） ，由參熔合的N - allylacetamide與hrucl （ pph3 ） 3 ，在苯下，氬氣為40小時。 The l-propenylacetamide was isolated by distillation. L型propenylacetamide分離蒸餾。
In a drybox, an ampule was charged with 1- propenylacetamide (0.2103 g, 2.15在一個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.和攪拌棒。
The ampule was removed from the drybox and tert-butyl該安瓿被拆掉，從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.加入下一個氬氣使用schlenk技術。 The ampule was then degassed, sealed under vacuum and placed in a 1500C oil bath.該安瓿當時脫氣，密封真空條件下，並放置在一個1500c油浴。 After several hours the ampule contents were dissolved in DMF, precipitated into acetone and dried in vacuo.經過幾個小時的安瓿內容被解散在DMF ，沉澱成丙酮和乾果在真空中。
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.在一個drybox ，反應瓶被落案控以1 -p ropenylacetamide（ 0 .2505克， 2 .56m mol） ，苯（ 0 .5毫升）和攪拌棒。 The flask was then sealed with a septa and removed from the drybox.瓶子是密封，然後與一隔，並取消從drybox 。 A solution of ZnCl2 (25解決氯化鋅（ 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 -二氯乙烷被添加到燒瓶通過注射器。 After several hours at room temperature the contents became very viscous.後幾個小時，在室溫下的內容，成為粘性非常大。 The contents were then dissolved in DMF, precipitated into acetone, and dried in vacuo,, having the formula (23).內容，然後溶解於二甲基甲醯胺，沉澱成丙酮，和乾果在真空中， ，有公式（ 23 ） 。
An alternative procedure was also used.另一種程式，還採用了。 In a drybox, a reaction vial was charged with 1- propenylacetamide (0.2018 g, 2.06在一個drybox ，反應小瓶被落案控以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）和攪拌棒。 The mixture was allowed to stir in the drybox for several days.混合物被允許轟動，在drybox數天。 The vial contents were dried in vacua.該小瓶的內容，乾燥，在vacua 。
EXAMPLE 7例如7 Poly(l-propenylacetamide-co-maleimide) 聚（ L - propenylacetamide -合作-醯亞胺） In a drybox, a reaction vial was charged with maleimide (0.0969 g, 1.00在一個drybox ，反應小瓶被落案控以馬來醯亞胺（ 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.和攪拌棒。 A solution of AIBN解決aibn (0.01 M) in benzene was prepared. （ 0.01 m ）在苯的準備。 The AIBN solution (0.50 Ml, 5.0 x該aibn解決方案（ 0.50毫升， 5.0 x 10-4 10月4日 mmol) mmol ） was then added to the vial containing the monomers.當時添加到小瓶含有單體。 The vial was capped, sealed with TEFLONS tape, and quickly brought out of the drybox and placed in the photolysis chamber.該小瓶被限制，密封與teflons磁帶，並迅速帶出的drybox並放置在光廳舉行會議。 During photolysis at 366 nm, the polymer precipitated from solution.在光在366 nm時，聚合物沉澱，從解決方案。 The polymer was isolated by precipitation into diethyl ether and dried in vacuo, and had the formula (24).聚合物分離沉澱到乙醚和乾果在真空中，並已公式（ 24 ） 。
Additionally, thermolysis of the initiator was also effective for the copolymerization of the enamides.此外，熱的發起者，也是有效的為共聚的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.所採用的程式是一樣的，除了上述反應混合物被密封在一安瓿真空條件下並放置在一油浴在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在一個drybox ，反應小瓶被落案控以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和轟動 bar.大律師公會。 The vial contents were stirred and solidified overnight, to give polymer (25).該小瓶的內容分別為攪拌和凝固在一夜之間，讓聚合物（ 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.該均聚物和共聚物的發明具有商業實用工具，包括但不限於已知的套用乙烯醯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.舉例來說，這些聚合物的套用在紡織，粘合劑和塗料，造紙，石油，水處理，化妝品，工業和製藥工業。 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.這些聚合物有更廣泛的套用，比父母聚（乙烯胺） ，因為小說烷基側鏈附於候補的立場聚合物的骨幹提供了一個補充，多樣性的組成部分，以新的聚合物，這使得性能的聚合物，例如，溶解度，要專門為一理想的使用。
For example, an n-butyl group attached at every other position of the polymer backbone would increase solubility in non-polar solvents, eg, hydrocarbons.舉例來說，一個正丁酯集團十分重視在每一個其他的立場，聚合物的骨幹，將增加的溶解度在非極性溶劑中，例如，碳氫化合物。 A substituted aryl, eg, 4-phenol, attached at every other取代芳基，例如， 4 -苯酚，重視每一個其他 position of the polymer backbone would increase the solubility in polar organic solvents, eg, ethyl acetate.的立場，聚合物的骨幹，將增加的溶解度在極性有機溶劑，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.具體套用聚合物本發明的，可以包括flocculence加強在檔案中製造業和水處理，及維修高粘度石油產品，以方便抽水。 The polymers can also be used to prepare ion- exchange membranes.聚合物也可以被用來編寫離子交換膜。
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.其他的體現，這是可以理解的同時，該發明已被描述在與詳細的說明，即前述說明的用意是說明，而不是限制的範圍所附的索賠。 Other aspects, advantages, and modifications are within the scope of the following claims.其他方面的優勢，和修改都在範圍下列索賠。
