CN107683357A - Efficient wet-strength resins from novel crosslinker - Google Patents

Abstract

Fortified resin and production and preparation method thereof.Fortified resin can include the polyamine partial cross-linked with bridging part and have azetidinium ions.Bridging part can be derived from symmetrical crosslinking agent in function.Symmetrical crosslinking agent can include diisocyanate, the diketone of 1,3 dialkyl group diazetidine 2,4, dianhydride, diacyl halogen, dienone, dialkyl group halogen or its any mixture in function.

Description

Efficient wet-strength resins from novel crosslinker

Technical field

Disclosed embodiment is usually directed to fortified resin.More specifically, these embodiments are related to fortified resin, and it can be with Including the polyamine partial cross-linked with bridging part and there are azetidinium ions, wherein bridging part can come from function Symmetrical crosslinking agent with and production and preparation method thereof.

Background technology

Paper is the sheet material containing the small-sized discrete fibre being connected with each other.Fiber is generally by dilute water slurry or slurries in dusting cover Upper formation sheet.Although using synthetic fibers once in a while, paper is generally made up of cellulose fibre.By undressed cellulose fiber Paper products made of dimension promptly lose its intensity when getting wet, i.e. they have " wet strength " of very little.Common paper it is wet strong Degree only has about the 5% of its dry strength.The wet strength of paper is defined as the resistance to rupture of paper or anti-disintegrative when being spontaneously wet out by water.Ginseng See U.S. Patent No. 5,585,456.In order to overcome this shortcoming, the method for various processing paper products has been employed.

Wet-strength resins applied to paper can be " permanent " type or " interim " type, and this is to be kept by paper after being immersed in the water What the time of its wet strength defined.Although wet strength conservation rate is desired feature in packaging material, due to The paper products of this feature could only degrade under undesirable harsh conditions, so handling problems be present.Some resins have Temporary transient wet strength is simultaneously applied to toilet paper purposes or disposable paper purposes；But these resins often suffer from one or more Shortcoming.For example, the wet strength of resin generally has low amounts value (the about accessible horizontal half of permanent type resin), resin is easy Corroded by mould and mucus, and/or resin can only be prepared into weak solution.

The conventional resins of permanent wet strength can be provided for paper generally by using epichlorohydrin (B) (" epi ") modified polyamide Base amine polymer (such as A) is to form Polyamide amine (PAE)-epichlorohydrin resins to obtain.

Conventional resins synthesis utilizes the difunctionality property of epichlorohydrin, to be crosslinked and be produced using epoxide group and cl radical Both quaternary nitrogen sites.In these conventional resins, the asymmetric functional group of epichlorohydrin causes after its epoxy radicals is reacted with secondary amine Open loop, then chloropharin pendant side group moiety intramolecular cyclization with produce azetidine functional group or with another Polyamide amine point Intermolecular (crosslinking) occurs for son.Therefore, the first step for reacting Polyamide amine prepolymer A and epichlorohydrin B is relatively low At a temperature of epoxy ring-opening made by the secondary amine group of pre-polymer backbone.Produce the novel functionalized polymer with chloropharin side base C, and the technique typically results in the little or no significant changes of prepolymer molecular weight.

Second step is related to two competitive reactions of chloropharin side base：1) cation azetidinium Chloride functional group is produced Intramolecular cyclization, without the increase for observing molecular weight；With the intermolecular alkylated reaction for 2) making crosslinked polymer, it is aobvious Writing ground increases its molecular weight.The result of two kinds of reactions is all described in PAE- epichlorohydrin resins structures D.In fact, epichlorohydrin Alkylation, intramolecular cyclization and cross-linking reaction occur simultaneously, but speed is different.

Finished product wet strength polymer product contains a small amount of remaining chloropharin side base as shown in structure D and has 2- hydroxyl-functionals The 3- carbon crosslinked groups of group, and a considerable amount of quaternary nitrogen heterocycles butane chloride functional group.The product can also contain a large amount of Epichlorohydrin hydrolysate 1,3-DCP and 3-CPD.

Three key reactions in the conventional method, i.e. chloropharin side base form (open loop), are cyclized into azetidinium ions base Group's (cationization) and crosslinking (intermolecular alkylation), relative speed when carrying out at room temperature respectively is about 140:4:1.Cause This, chloropharin side base is quickly formed by the ring-opening reaction of secondary amine in epichlorohydrin epoxides and prepolymer.The first step compared with Carried out at low temperature (for example, about 25 DEG C to 30 DEG C).

In second step, chloropharin group is will be relatively slowly cyclized to form cationic nitrogen azetidine group.It is even more slow Ground crosslinks, such as carries out in the following manner：1) such as tertiary amine of chloropharin side base reacts with secondary amine moieties；And/or 2) uncle The intermolecular alkylation of amine and chloropharin pendant side group moiety.

In order to keep the actual utility of most short reaction circulation time, traditional manufacture method usually requires heating response mixing Thing is to improve reaction rate, such as is heated to about 60 DEG C to about 70 DEG C.Generally, reaction and in highly filled lower progress, with Reactor output is maximized, and finished product wet-strength resins are provided with can energy minimization cost of transportation under highest solid.It is high Concentration is advantageous to slower intermolecular reaction.It is anti-between intramolecular cyclization and crosslinking under these high temperature and High Concentration Situation Speed is answered to become competitive.Therefore, the problem run into classical production process be cross-linking reaction speed become enough to Soon to be issued to required viscosity terminal (molecular weight) as cost in formation azetidinium ions group.If allow reaction after Continuous to exceed required viscosity terminal to produce higher levels of azetidine group, then reactant mixture may gelation and shape Into solid matter.

Because high azetidine group content and HMW can be used in the maximum wet strength efficiency of PAE resin, institute Maximized with the formation and crosslinking wishing to make azetidine group without making product gel or providing the gel during storage The product of change.These conditions, plus the requirement to high solid to minimize cost of transportation, limit to form efficient wet strength The many aspects of resin product.

Therefore, it is necessary to improved fortified resin, such as assigning the wet strength of paper products proper level, and its manufacture And application method.

The content of the invention

Provide fortified resin and production and preparation method thereof.In at least one example, fortified resin can include with The partial cross-linked polyamine in bridging part and there are azetidinium ions.Bridging part can come from symmetrically being crosslinked in function Agent.In function symmetrical crosslinking agent can be or including diisocyanate, 1,3- dialkyl group diazetidine -2,4- diketone, Dianhydride, diacyl halogen, dienone, dialkyl group halogen or its any mixture.

In at least one example, the method for manufacturing fortified resin can include making polyamine with symmetrically handing in function Connection agent is reacted to produce partial cross-linked polyamine.Symmetrical crosslinking agent can be or including diisocyanate, 1,3- bis- in function Alkyl diazetidine -2,4- diketone, dianhydride, diacyl halogen, dienone, dialkyl group halogen or its any mixture.Hand over part The polyamine of connection can be reacted with epihalohydrin to produce the fortified resin with azetidinium ions.

In at least one example, the method for strengthening paper can include making fiber contact with fortified resin.Strengthen tree Fat can be or including the polyamine partial cross-linked with bridging part and have azetidinium ions.Bridging part can come from Symmetrical crosslinking agent in function.Symmetrical crosslinking agent can be or including diisocyanate, 1,3- dialkyl group diazas in function Cyclobutane -2,4- diketone, dianhydride, diacyl halogen, dienone, dialkyl group halogen or its any mixture.

Embodiment

Fortified resin, such as wet-strength resins are provided, the technique for manufacturing fortified resin, and handled using fortified resin Paper is to assign the technique of intensity.Using the crosslinking agent of symmetrical (" symmetrical ") and optional simple function modifying agent in function and by polyamine Reaction and the reaction of partial cross-linked polyamine and epihalohydrin (such as epichlorohydrin) with symmetrical crosslinking agent in function separate, point Into multiple discrete steps, there is provided there is the performance of enhancing and/or the novel reinforced resin of improved synthesis flexibility, for example (,) it is wet Intensity resin.In addition to providing the wet tensile generally improved progress relative to prior art, the product and method can provide Higher azetidinium ions content, the reactive functionalization of additional levels, maximized molecular weight and/or good storage Stability.

Polyamine crosslinking is different from " cationization " technique that halo is alcohol functionalized and is cyclized, and this is to customize functionalized cationic Degree, molecular weight and/or other resin properties provide the feature of substantial flexibility.For realizing crosslinking and the functionalization of polyamine Function on symmetrical crosslinking agent and optional simple function modifying agent can be differently configured from examination for assigning resin cationic charge Agent.Specifically, can be by the reaction of symmetrical crosslinking agent on polyamine and function and partial cross-linked polyamine and epihalohydrin Reaction separates.For example, can be in the first step using the crosslinking agent of (or abbreviation " symmetrical ") symmetrical in function, it can be provided The substantive control of cross-linked structure and property to partial cross-linked prepolymer (such as polyamine or Polyamide amine prepolymer).To The step of resin imparting cationic charge (" cationization " technique), any epihalohydrin (such as epichlorohydrin) can be used to produce Azetidinium ions functional group.

Compared with common amount in the traditional Polyamide amine-epichlorohydrin fortified resin that can not be prepared by the technique, it is used for The method of manufacture fortified resin can also reduce the amount of epichlorohydrin by-products.For example, fortified resin can have it is essentially decreased The horizontal chloro- 2- propyl alcohol of 1,3- bis- (1,3-DCP or " DCP ") and 3- chloropropane -1,2- glycol (3-CPD or " CPD "；Same generation The MCPD of list chloropropane glycol), it is generally synthesized along with epichlorohydrin wet-strength resins.

In some instances, for manufacture the method for fortified resin (such as wet fortified resin) may include to make polyamine (its It is referred to alternatively as polyamine prepolymer herein) reacted with symmetrical crosslinking agent in function so that partial cross-linked polyamine is made.So, gather Amine can be partial cross-linked with bridging part, and bridging part can come from symmetrical crosslinking agent in function.Can be by table halo Alcohol is added in partial cross-linked polyamine so that the alcohol functionalized polymer of halo is made.The alcohol functionalized polymer of halo can be with ring Change and form the resin with azetidine moiety.So, fortified resin can be or including partial cross-linked with bridging part Polyamine and there is azetidinium ions or part.

If desired, the technique may further include make polyamine and deficiency comprising secondary amine reactivity part Simple function modifying agent reacts.If polyamine and the simple function modifying agent of deficiency react, reaction can be in polyamine and symmetrical crosslinking Before agent reaction, during or after or occurred with the various combinations of these times.

In an example, polyamine can have following structure：

Wherein R can be alkyl, hydroxyalkyl, amine, acid amides, aryl, heteroaryl or cycloalkyl.In structure P, w can be 1 To about 10,000 integer.As defined part provided, R group (such as " alkyl " or " hydroxyalkyl ") is providing chemical valence The convenient description that traditional rule is applicable；Therefore, structure P R can be described as alkyl or hydroxyalkyl, and it is reflecting " R " base Group is divalence and can alternately be described as alkylidene or hydroxy alkylidene.

Most widely used and maximally effective wet-strength resins product is typically derived from the Polyamide amine with epichlorohydrin reaction (PAA) prepolymer, to form so-called Polyamide amine-epichlorohydrin (PAE) resin.Therefore, when polyamine is or comprising polyamide During base amine prepolymer, it is desirable to which resin is not limited to the system based on Polyamide amine, but (poly- available for any amine-containing polymer Amine), such as structure P and other amine-containing polymers.

Epichlorohydrin has different, the therefore difunctional of the chemical functional group of " asymmetry ", epoxy radicals and cl radical Compound.This asymmetric functional group causes epichlorohydrin open loop when with epoxy reaction with secondary amine, then chloropharin side base Part is used for：1) intramolecular cyclization is to produce cationic nitrogen azetidine functional group；Or 2) intermolecular cross-linking polymer to increase Molecular weight.Epichlorohydrin resins structure D illustrates the result of two kinds of reactions in Polyamide amine-epichlorohydrin (PAE) resin.

Present disclose provides the preparation and technique for preparing fortified resin (such as wet-strength resins), and it has from increasing It is the horizontal cationic charge (higher charge density) of the increase of strong azetidinium ions content, extra degree of functionality, excellent Change or maximized molecular weight, highly filled, and/or low concentration DCP and CPD.In an aspect, disclosed side Resins synthesis is divided into two single and controllable steps by method.The first step forms the crosslinkable prepolymer of intermediate molecular weight, and it is logical Crossing makes polyamine prepolymer be reacted with symmetrical crosslinking agent in function and prepares.It is different from the function of asymmetric crosslinking agent epichlorohydrin, The symmetrical crosslinking agent of the disclosure is reacted to be crosslinked using identical part with two prepolymer secondary amine groups.If desired, Or period forward and backward in cross-linking step simple function group can be used, to assign without the extra functional group of the prepolymer of crosslinking function. Second step using epichlorohydrin with by using the epichlorohydrin of decrement so that the azetidinium ions on polymer form maximum Change to assign Cationic functional groups, without any crosslinking function.This technique is with traditional practice on the contrary, this is constrained to The azetidinium ions for needing optimization to compete are formed and simultaneous cross-linking mechanism.

Polyamine prepolymer

A series of polyamine (polyamine prepolymer) may be used as the precursor of wet-strength resins disclosed herein.Polyamine can be or Including the primary amine moiety and/or secondary amine moieties being connected with least one interval base.

For example, in an aspect, the polyamine for being referred to herein as polyamine prepolymer can have following structure：

Wherein R can be such as alkyl, hydroxyalkyl, amine, acid amides, aryl, heteroaryl or cycloalkyl.In structure P, w can To be the integer from 1 to about 10,000,1 to about 5,000,1 to about 3,000,1 to about 1,000,1 to about 100 or 1 to about 10.This " R " group a bit, such as " alkyl " providing to by removing one or more hydrogen atoms (such as specific base in form from precursor group Group needed for) derived from special groups simple description.Therefore, the tradition rule of term " alkyl " applied chemistry valence state in structure P Then apply, but by including for example (coming from one by " the alkane diyl " that removes two hydrogen atoms in form from alkane to be formed Two hydrogen atoms of individual carbon atom or a hydrogen atom from two different carbon atoms).Unless otherwise indicated, this alkyl can Can be non-annularity or cyclic group, and/or can be straight or branched to be substituted or unsubstituted group." hydroxyl alkane Base " group is included in one or more hydroxyls (OH) part substituted on defined " alkyl ".

In this aspect of the invention and unless otherwise indicated, structure P R can be the alkyl portion of straight chain (straight chain) or side chain Point.Part R can also be cycloalkyl, that is, have the cyclic hydrocarbon moieties of from 1 to about 25 carbon atom.For example, R can have from 1 to 25th, from 1 to 20, from 1 to 15, from 1 to 12, from 1 to 10, from 1 to 8, from 1 to 6 or from 1 to 4 carbon atom.Same citing and Speech, R can have from 2 to 10,2 to 8,2 to 6 or 2 to 4 carbon atoms.In further, R can be C₁Partly, C₂ Partly, C₃Partly, C₄Partly, C₅Partly, C₆Partly, C₇Partly, C₈Partly, C₉Partly, C₁₀Partly, C₁₁Partly,_C12Partly, C₁₃ Partly, C₁₄Partly, C₁₅Partly, C₁₆Partly, C₁₇Partly, C₁₈Partly, C₁₉Partly, C₂₀Partly, C₂₁Partly, C₂₂Partly, C₂₃Portion Divide, C₂₄Partly, C₂₅Partly, C₂₆Partly, C₂₇Partly, C₂₈Partly, C₂₉Partly, C₃₀Part.

In the polyamine with said structure P, R can also be more primary amine, such as polyvinylamine and its copolymer.Can be with structure Example into more primary amine of the R in structure P includes but is not limited to following structure, and is total to alkene and other unsaturated parts Polymers, wherein n can be the integers from 1 to about 25：

Alternately, n can be the integer from 1 to about 20,1 to about 15,1 to about 12,1 to about 10 or 1 to about 5.Another In one side, n can be 1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19,20,21,22, 23rd, 24 or 25.

The suitable polyamine (polyamine prepolymer) of resin for preparing the disclosure includes but is not limited to polyalkylene polyamine, Such as poly- ethylene polyamine, including diethylenetriamines (DETA), trien (TETA), aminoethylpiperazine, four Asias The amine of ethyl five, penten, N- (2- amino-ethyls) piperazine, N, N- double (2- amino-ethyls) ethylenediamine, diamino ethyls Triamido ethamine, piperazine ethyl trien etc..Polyamine for preparing the resin formulation for the disclosure also includes second Diamines, low molecular polyamides base amine, polyvinylamine, polyethyleneimine (PEI) and vinylamine and other unsaturations are copolymerizable The copolymer of monomer (such as vinyl acetate and vinyl alcohol).

According to polyamine prepolymer P one side, w corresponds to the polyamine prepolymer from about 2,000 to about 1,000,000 The number range of Mw molal quantitys.Polyamine prepolymer P Mw molecular weight can also be from about 5,000 to about 750,000, about 7,500 To about 500,000, about 10,000 to about 200,000, about 20,000 to about 150,000 or about 30,000 to about 100,000.

Polyamide amine prepolymer

According to the disclosure, a series of Polyamide amine prepolymers are also used as the precursor of wet-strength resins.Polyamide-based Amine prepolymer can pass through polyalkylene polyamine and dicarboxylic acids with least two primary amine groups and at least one secondary amine group Reacted in the technique for forming the long-chain polyamide containing recurring group disclosed herein to be made.In an aspect, polyamides Amido amine prepolymer can have following structure：

Wherein R¹It is (CH₂) m, wherein m be 2,3,4 or 5；R²It is (CH₂) n, wherein n be 2,3 or 4；W is 1,2 or 3；P is Corresponding to the number range of the Polyamide amine prepolymer Mw molecular weight from about 2,000 to about 1,000,000.Mw molecular weight also may be used Think from about 5,000 to about 100,000, about 7,500 to about 80,000, about 10,000 to about 60,000, about 20,000 to about 55, 000 or about 30,000 to about 50,000.

In an aspect, Polyamide amine prepolymer can have following structure：

Wherein R³For (CH₂)_q, wherein q scopes are from 0 to 40；R correspond to from about 2,000 to about 1,000,000 it is poly- The number range of amido amine prepolymer Mw molecular weight.Similarly, Mw molecular weight can also be from about 5,000 to about 100.000, About 7,500 to about 80,000, about 10,000 to about 60,000, about 20,000 to about 55.000 or about 30,000 to about 50,000. Therefore, in structure (CH₂)_qIn, q scopes can also be from 0 to about 40,0 to about 35,0 to about 30,0 to about 25,0 to about 20,0 to About 15,0 to about 12,1 to about 40,1 to about 35,1 to about 30,1 to about 25,1 to about 20,1 to about 15,1 to about 12,1 to about 10, 1 to about 8 or 1 to about 6.

In another example, Polyamide amine prepolymer can have following structure：

Wherein n is 1 to 8；P is 2 to 5；And m is 0 to 40, and similar molecular weight ranges are applicable.

As disclosed, suitable Polyamide amine is generally by making dicarboxylic acids (diacid) or its corresponding dicarboxylic acids halogenation Thing or diester are reacted with polyamine (such as polyalkylene polyamine) to prepare.Suitable polyamine can be used as including those disclosed herein The polyamine (polyamine prepolymer) of the precursor of wet-strength resins in itself.For example, useful Polyamide amine can be suitable by making Polyalkylene polyamine, such as poly- ethylene polyamine, including ethylenediamine in itself, diethylenetriamines (DETA), trien (TETA), aminoethylpiperazine, tetren, penten, N- (2- amino-ethyls) piperazine, double (the 2- ammonia of N, N- Base ethyl)-ethylenediamine, diamino ethyl triamido ethamine, piperazine ethyl trien etc. and polycarboxylic acid, such as amber Acid, glutaric acid, 2- methylsuccinic acids, adipic acid, pimelic acid, suberic acid, azelaic acid, decanedioic acid, heneicosanedioic acid, dodecane two Acid, 2- methylglutaric acids, 3,3- dimethylated pentanedioic acids and three carboxyl pentanes, such as 4- carboxyl pimelic acid；Alicyclic saturated acid, example Such as 1,2- cyclohexane dicarboxylic acids, 1,3- cyclohexane dicarboxylic acids, 1,4- cyclohexane dicarboxylic acids and 1,3- cyclopentane dicarboxylic acids；It is unsaturated Aliphatic acid, such as maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, aconitic acid and hexane -3- diacid；Unsaturated alicyclic ring Race's acid, such as Δ 4- cyclohexene dicarboxylic acids；Aromatic acid, such as phthalic acid, M-phthalic acid, terephthalic acid (TPA), 2,3- naphthalenes Dioctyl phthalate, benzene-Isosorbide-5-Nitrae-oxalic acid and heterolipid race acid, such as diglycolic acid, thiodiglycol acid, two thiodiglycols acid, imino-diacetic Acetic acid and methyliminodiacetic acid reaction are made.Generally, there is formula RO₂C(CH₂)_nCO₂R (wherein n=1 to 10 and R=H, first Base or ethyl) diacid and its related diester and its mixture be preferable.Adipic acid is readily available and is commonly used.

Other suitable polyamine can include can be from the JEFF that Huntsman is boughtPolyetheramine.JEFFPolyetheramine includes the primary amino radical for being connected to polyether backbone end.Polyether backbone is based on expoxy propane (PO), epoxy Ethane (EO) or mixing EO/PO.Other JEFFProduct can contain other backbone segments, and can have and pass through resistance Hinder primary amine or different reactivity is provided by secondary amine functional groups.The JEFF of low molecule amountSuch as JEFFD-230, and the JEFF of higher molecular weightSuch as JEFFD-2000 is acceptable.

Symmetrical crosslinking agent

Generally, the secondary amine of polyamine can react with one or more symmetrical crosslinking agents.In an example, the secondary amine of polyamine Reaction with symmetrical crosslinking agent can provide the control to the higher degree of cross-linking process, and with higher compared with beginning prepolymer The middle crosslinkable prepolymer of molecular weight.The viscosity terminal of intermediate and molecular weight therefore can be at least partially through being made The amount of symmetrical crosslinking agent is easily predefined and controlled.Cross-linking reaction can proceed to terminal when crosslinking agent consumes And run out of full-time stopping when crosslinking agent.The reduction of secondary amine functional groups and measurable amount will keep can be used for further function Change.

In the cross-linking step, based on the total amount of the secondary amine available for crosslinking, polyamine can be with the symmetrical crosslinking agent of deficiency Reaction, to provide partial cross-linked polyamine.Therefore, partial cross-linked polyamine has the molecular weight higher than polyamine, even if it is The intermediate of the technique, and it remains a part of secondary amine group being present in polyamine.In further, because The symmetrical crosslinking agent of the stoichiometry less than 50% can be used, is present in so partial cross-linked prepolymer retains in polyamine Most of secondary amine group.

Based on prepolymer repeat unit with the single secondary amine and symmetrical crosslinking agent reacted with two reactivity The stoichiometric reaction of part, prepolymer and crosslinking agent needs 2:1 mol ratio, and in fact, use 2:1 or higher mole The prepolymer and crosslinking agent of ratio.In an aspect, the mol ratio of symmetrical crosslinking agent and prepolymer can be selected to be more than to provide 0%, but less than 50%, less than 45%, less than 40%, less than 35%, less than 30%, less than 25%, less than 20%, be less than 15%th, less than 10%, less than 5%, less than 4%, less than 3%, less than 2%, less than 1%, less than 0.75% or less than 0.5% The stoichiometric proportion of crosslinking agent and prepolymer.These values are reflected using integral molar quantity during more than one symmetrical crosslinking agent.

Polyamine can react in the presence of water or in the absence of water with symmetrical crosslinking agent.In an example, polyamine can To be reacted with symmetrical crosslinking agent in water-bearing media (such as water or aqueous mixture).In another example, polyamine can be with Symmetrical crosslinking agent reacts in non-aqueous medium (such as non-aqueous solvent or diluent).In another example, polyamine can be with Reacted with symmetrical crosslinking agent in the absence of any other liquid medium (no matter aqueous or non-aqueous).Non-aqueous medium (such as solvent or diluent) can not react with polyamine, symmetrical crosslinking agent and/or partial cross-linked polyamine.If polyamine is non- React in water-bearing media or with symmetrical crosslinking agent under in the absence of any other liquid medium and handed over producing with bridging part part The polyamine of connection, then the polyamine partial cross-linked with bridging part remain free of or be substantially free of any water or can be mixed with water.

The example of symmetrical crosslinking agent can include but is not limited to one or more diisocyanate, one or more 1,3- bis- Alkyl diazetidine -2,4- diketone, one or more dianhydrides, one or more diacyl halogen, one or more dienones, One or more dialkyl group halogen or its any mixture.Other examples of symmetrical crosslinking agent can include but is not limited to a kind of or more Kind diacrylate compounds, one or more double (acrylamide) compound, one or more diepoxides, one kind or more The poly- azetidine compounds of kind, one or more N, N'- methylene-bis--Methacrylamide, one or more poly- (alkylenes Base glycol) diglycidyl ether or its any mixture.In at least one example, symmetrical crosslinking agent can include it is following at least It is a kind of：(1) diisocyanate, 1,3- dialkyl group diazetidine -2,4- diketone, dianhydride, diacyl halogen, dienone and dioxane Base halogen and following at least one：(2) diacrylate compounds, double (acrylamide) compounds, diepoxide, poly- azacyclo- Butane compound, N, N'- methylene-bis--Methacrylamide and poly- (aklylene glycol) diglycidyl ether.

Diisocyanate can not be blocked or block.Illustrative uncapped diisocyanate can include but is not limited to 4, 4'- methylenediphenyl diisocyanates (methylenediphenyl diisocyanates, MDI)；Toluene-2,4-diisocyanate, 4- diisocyanate (first Phenylene diisocyanate, TDI)；1,6- hexane diisocyanate (hexamethylene diisocyanate, HDI)；5- isocyanato-s -1- (isocyanatomethyl) -1,3,3- trimethyl-cyclohexanes (IPDI, IPDI) or its any mixture. Illustrative end-blocking diisocyanate can include but is not limited to the isocyanide of 4,4'- methylenediphenyls two of double caprolactam blockings Acid esters；The 4 of 4,4'- methylenediphenyl diisocyanates two (2- diacetylmonoximes) adduct, double (3,5- dimethyl pyrazoles) end-blocking, 4'- methylenediphenyl diisocyanates or its any mixture.The diisocyanate of commercially available end-blocking can be included but not It is limited to be purchased from Baxenden Chemicals'BI products, such asBI 7641、7642、 7674th, 7675,7950,7951,7960,7961,7963 and 7982, and it is purchased from the RUCO-Guard productions of Rudolf groups Product, such as RUCO-Guard XCR, XTN, FX 8011, FX 8021, NET, TIE and WEB.

Illustrative 1,3- dialkyl group diazetidine -2,4- diketone can include but is not limited to 1,3- diazacyclo fourths Alkane -2,4- diketone；1,3- dimethyl -1,3- diazetidine -2,4- diketone；1,3- diethyl -1,3- diazetidines - 2,4- diketone；1,3- diphenyl -1,3- diazetidine -2,4- diketone；Or its any mixture.Illustrative dianhydride can be with Including but not limited to pyromellitic acid anhydride；Ethylene glycol is double (trimellitic anhydride)；4,4'- bisphenol A dianhydrides or its any mixture. Illustrative diacyl halogen can include but is not limited to oxalyl chloride, oxalyl bromine, succinyl chloride, benzene -1,2- dicarbapentaborane dichloro, benzene - 1,2- dicarbapentaborane bromine, o-phthaloyl chloride or its any mixture.It is pungent that illustrative dienone can include but is not limited to 1,7- Diene -3,6- diketone；Double (2- propylene -1- ketone)-(1,4- benzene) or its any mixture.Illustrative dialkyl group halogen can include But it is not limited to 1,2- dichloroethanes；Glycol dibromide；1,2- ethylidene periodides；1,2- dichloropropanes；1,2- dibromopropanes；1,3- Dichloropropane；1,3- dibromopropanes；1,3- diiodo propanes；Double (chloromethyl) benzene of 1,4-；Double (bromomethyl) benzene of 1,4- or its is any Mixture.

Other useful symmetrical crosslinking agents can include but is not limited to following any one or more：

Wherein R⁴It is (CH₂)_t, and wherein t is 1,2 or 3；

Wherein x is from 1 to about 100；

Wherein y is from 1 to about 100；

Wherein x'+y' is from 1 to about 100；With/ Or

Wherein z is from 1 to about 100；Including its any combinations.

The instantiation of symmetrical crosslinking agent can be or including N, N'- methylene-bis-acrylamides, N, N'- methylene- Double-Methacrylamide, PEG diglycidyl ether, poly- (propane diols) diglycidyl ether, the propylene of polyethylene glycol two Acid esters, poly- azetidine compounds and its any combinations.

According to further aspect, symmetrical crosslinking agent can be selected from or can have what can be reacted with secondary amine including some The polymer or copolymer of functional moiety's type, you can for use as the symmetrical crosslinking agent according to the disclosure.In an aspect, this It can be the polymer or copolymer for including azetidine functional group to polymerize symmetrical crosslinking agent a bit.These polymerize symmetrical crosslinking agent Can be such as acrylate, methacrylate, alkene, diene with azetidine functionalized monomer (such as 1- isopropyls Base -3- (methacryloxy) -1- methyl azetidine chlorine Q or 1,1- diallyl -3- hydroxy azetidine chlorine R, Its structure is as shown in the figure) copolymer.

Polymerizeing symmetrical crosslinking agent can also be or can include such as acrylate, methacrylate, alkene, diene With the copolymer of other azetidine functionalized monomers (such as compound S, T or U, as shown in text).

In this aspect of the invention, symmetrical crosslinking agent may be selected from or may include acrylate, methacrylate, alkene or diene With the copolymer of the azetidine functionalized monomer selected from Q, R, S, T, U and combinations thereof, azetidine wherein in copolymer- Functionalized monomer and acrylate, methacrylate, the ratio of alkene or diene monomers can be from about 0.1% to about 12%.In further, azetidine functionalized monomer and acrylate, methacrylate, alkene in copolymer The ratio of hydrocarbon or diene monomers can be from about 0.2% to about 10%, about 0.2% to about 10%, about 0.5% to about 8%, about 0.75% to about 6% or about 1% to about 5%.The example of symmetrical the crosslinking agent polymer and copolymer of these types may refer to Below with reference to document：Y.Bogaert, E.Goethals and E.Schacht,《Equine Larmor chemistry (Makromol.Chem.)》,182,2687-2693(1981)；M.Coskun, H.Erten, K.Demirelli and M.Ahmedzade,《Depolymerization and stably (Polym.Degrad.Stab.)》,69,245-249(2000)；And the U.S. Patent the 5,510,004th.

According on one side, symmetrical crosslinking agent can be selected from or can include azetidine-functionalization of bottom line Polyamide amine.That is, Polyamide amine can have the azetidine functionalization of bottom line, it is this type Symmetrical crosslinking agent in reactivity part.In this case, crosslinking function is by can be with Polyamide amine prepolymer The azetidine moiety of secondary amine reaction is realized.Suitable for preparing azetidine-functionalized polyamides' base amine of bottom line Polyamide amine be that can be used for preparing the identical general structure and formula of resin in itself, structure X, Y as described herein and Z.Following structure illustrates a reality of the azetidine functionalized polyamides' base amine for being suitable for the bottom line of symmetrical crosslinking agent Example：

It is from about 10 to about 1000 that wherein p, which is equal to or more than 2, q/p ratios, and the structure is included being crosslinked, and By at least two azetidine moieties that such as X Structural Identification is symmetrical crosslinking agent in function.As q/p ratios show, Compared with acid and amine residue, the azetidine moiety of sub-fraction be present.In addition, Polyamide amine X can also have wherein q/p Ratio is about 12 to about 500, about 14 to about 400, about 16 to about 300, about 18 to about 200 or the structure of about 20 to about 100.It is a kind of The azetidine of the bottom line of type-functionalized polyamides' base amine for example provides in U.S. Patent No. 6,277,242.

As shown in the mol ratio of symmetrical crosslinking agent and polyamine (such as PAE prepolymers), generally, relatively small portion it is available secondary Amine site experience is crosslinked to form side chain or partial cross-linked Polyamide amine prepolymer.Except provided herein is mol ratio in addition to, For example, the mol ratio of symmetrical crosslinking agent and prepolymer can be selected to provide crosslinking agent and prepolymer from 0.01% to 5% Stoichiometric proportion.In further, the mol ratio of symmetrical crosslinking agent and prepolymer can provide from 0.1% to 4%, 0.2% to 3.5%, 0.3% to 3%, 0.4% to 2.5%, 0.5% to 2% or 0.6% to 1.5% crosslinking agent and prepolymer Stoichiometric proportion.These values are reflected using combination mole during more than one symmetrical crosslinking agent.

For example, using the Polyamide amine prepolymer derived from adipic acid and diethylenetriamines (DETA) as in fact Example, and use methylene-bis-acrylamide (MBA) crosslinkable prepolymer, partial cross-linked Polyamide amine prepolymer can by with Lower structure explanation：

Wherein RX bridgings part has following structure：

In addition to symmetrical crosslinking agent, the explanation, which does not reflect, uses any simple function modifying agent (hereafter).

Simple function modifying agent

The secondary amine group of polyamine can also react any required to assign prepolymer with one or more monofunctional compounds Chemical functional group.Monofunctional compound has can be with the reactive group of secondary amine or primary amine reaction and can be cation (to increase cationic charge density), hydrophily or hydrophobicity are (to adjust the phase interaction with the nonionic fragment of cellulose fibre With) non-reacted part.As needed, polyamine can be before the step of polyamine and the symmetrical crosslinking agent of deficiency react, the phase Between or afterwards, reacted with the simple function modifying agent comprising secondary amine reactivity part of deficiency.Further, with stoichiometry The reaction of the simple function modifying agent of deficiency can also use reaction or addition before, during or after being reacted with symmetrical crosslinking agent Any combinations carry out.

For example, in an aspect, simple function modifying agent can be selected from or can include neutral or cationic acrylate Compound, neutrality or cation acrylamide compound, acrylonitrile compound, monoepoxide or its any combinations.According to another On one side, simple function modifying agent may be selected from or may include alkyl acrylate, acrylamide, alkyl acrylamide, dialkyl group Acrylamide, acrylonitrile, 2- alkyl epoxies ethane, 2- (allyloxy alkyl) oxirane, hydroxyalkyl acrylates, ω-(third Alkene acyloxy)-alkyl trimethyl ammonium compounds, ω-(acrylamido)-alkyl trimethyl ammonium compounds and its any combinations. The example of simple function modifying agent is as follows.

For example, simple function modifying agent can be or including following at least one：Methyl acrylate；Acrylic acid alkyl Ester；Acrylamide；N methacrylamide；N, N- DMAA；Acrylonitrile；2- methyl oxiranes；2- ethyl rings Oxidative ethane；2- propyIoxiranes；2- (allyloxy methyl) oxirane；Acrylic acid 2- hydroxyl ethyl esters；Acrylic acid 2- (2- hydroxyls Ethyoxyl) ethyl ester；2- (acryloxy)-N, N, N- trimethyl second ammoniums；3- (acryloxy)-N, N, N- trimethyl propyl- 1- Ammonium；2- acrylamidos-N, N, N- trimethyl second ammonium；3- acrylamidos-N, N, N- trimethyl propyl- 1- ammoniums；With 1- isopropyls- 3- (methacryloxy) -1- methyl azetidine chlorine.According to the structure of modifying agent, it can be seen that in these compounds After secondary amine or primary amine reaction, cationic charge can be assigned to help to increase that cationic charge is close to the part of amine anergy Degree, thus it is possible to vary hydrophilic or hydrophobic property, such as to adjust the interaction with the nonionic fragment of cellulose fibre, and/or Other properties of crosslinkable prepolymer among gained can be influenceed.

Simple function modifying agent can with amount be from low about 0.0001 mole, about 0.0005 mole, about 0.001 mole, about 0.005 mole or about 0.01 mole paramount about 0.05 mole, about 0.07 mole, about 0.1 mole, about 0.15 mole or about 0.2 are rubbed The polyamine reaction of that/mole secondary amine group.For example, simple function modifying agent can be about 0.0001 mole to about 0.1 mole with amount/ The secondary amine group reaction of the polyamine of mole secondary amine group.

Halo alcohol functionalized polymers and intramolecular cyclization

Generally, by the way that the reaction of polyamine and crosslinking agent and the reaction of middle crosslinkable prepolymer and epichlorohydrin are separated, it is divided into Multiple discrete steps, compared with conventional method, second reaction step needs less epichlorohydrin to reach required terminal.Enter one Step, the second reaction step can be in the reaction conditions for being advantageous to optimize the formation of azetidine group rather than be further crosslinked Lower progress.The asymmetric functional group of epichlorohydrin is used for the functionalization to allow the relatively easy reaction of epoxy radicals and secondary amine, with Form chloropharin side base, the intramolecular cyclization of subsequent chloropharin side base is to generate cationic nitrogen azetidine functional group.The molecule of the latter Intramolecular cyclization can utilize the heating of halo alcohol functionalized polymers.

In an aspect, second reaction step can be carried out using any epihalohydrin, for example, epichlorohydrin, epibromohydrin and Epiiodohydrin or its any combinations.It is, for example, possible to use epichlorohydrin.When describing epichlorohydrin in the disclosure, for example, in structure or In reaction scheme, it should be noted that, any epihalohydrin can be used in the process.

For example, using the partial cross-linked Polyamide amine prepolymer derived from adipic acid and DETA described above It is crosslinked with using MBA, epichlorohydrin-functionalized product can be illustrated by following structure, and term is " halo is alcohol functionalized Polymer.”

As it was previously stated, in addition to symmetrical crosslinking agent, the explanation, which does not reflect, uses any simple function modifying agent.Epihalohydrin The reaction of (such as epichlorohydrin) is typically dedicated to consume high percentage or remaining secondary amine moieties to produce halohydrin functionalized poly Compound, it is chloropharin functionalized polymeric in this case.

The formation of halo alcohol functionalized polymers can be carried out using a range of epichlorohydrin molar ratios.For example, should Reaction can be carried out using the epichlorohydrin of excess.The stoichiometric reaction of epichlorohydrin and secondary amine group needs 1:1 mol ratio Epichlorohydrin and secondary amine.In an aspect, epichlorohydrin of the every mole of secondary amine from about 0.8 mole to about 3 moles can be used.It can replace Dai Di, epichlorohydrin, every mole secondary amine about 1.0 mole of the every mole of secondary amine from about 0.9 mole to about 2.5 moles can be used to about 2.0 moles, about 1.1 moles to about 1.7 moles, about 1.2 moles to about 1.5 moles, about 1.25 moles to about 1.45 moles of table Chloropharin.For example, the molal quantity of the epichlorohydrin of every mole of secondary amine can be about 0.8, about 0.9, about 1.0, about 1.1, about 1.2, about 1.3rd, about 1.4, about 1.5 or about 1.6.

The amount of symmetrical crosslinking agent and epihalohydrin can be enough the basic fortified resin for not having secondary amine group is made.The result It can be realized by using mole disclosed herein and ratio, still, exceed cited mole and ratio even if using Rate, the resin combination prepared by the disclosure can not also substantially include secondary amine group.For substantially free of secondary amine Group, it is intended that retain the initial secondary amine less than 10% in starting PAE resin before crosslinking, functionalization and positive ionization.It can replace Dai Di, can retain and be less than 5% in starting PAE resin, less than 2%, less than 1%, less than 0.5%, less than 0.2%, be less than 0.1%th, the initial secondary amine less than 0.01%, less than 0.005% or less than 0.001%.

Halohydrin (being usually chloropharin)-functionalized polymeric can be by making polymer undergo cyclisation conditions to form azepine Cyclobutane ion and change into wet-strength resins.Functionalized polymeric can be heated to form azetidinium ions.With wherein Heating causes crosslinking and cyclisation both conventional methods on the contrary, when being cyclized, the crosslink part of the technique be it is complete, by This provides bigger technology controlling and process and more suits the ability of the required property of gained resin.With conventional method on the contrary, being discussed herein The chloro- 2- propyl alcohol (1,3- of epichlorohydrin by-products 1,3- bis- being retained in resin can be reduced and/or minimized with the technique of description DCP or " DCP ") and 3- chloropropane -1,2- glycol (3-CPD or " CPD ") formation.

The concentration for the chloro- 2- propyl alcohol (1,3-DCP) of the epichlorohydrin 1,3- bis- under 25% solid being retained in fortified resin (DCP@25%) can be less than about 15,000ppm, less than about 14,000ppm, less than about 13,000ppm, less than about 12, 000ppm, less than about 11,500ppm, less than about 11,000ppm, less than about 10,500ppm, less than about 10,000ppm, be less than about 8,000ppm, less than about 6,000ppm or less than about 5,000ppm.

Following resin combination structure Z illustrate based on chloropharin functionalized polymeric Y shape illustrated above into quaternary nitrogen (" sun from Sonization ") cyclisation step result, it, which experienced, is enough to make chloropharin side base that intramolecular cyclization occurs to assign azetidine official The condition that can be rolled into a ball.

In the technique for forming resin combination, resin combination is by making halo alcohol functionalized polymers be subjected to foot The cyclisation conditions of azetidinium ions are formed to produce to convert halohydrin group.At least a portion halohydrin group can be with Cyclisation forms azetidinium ions or part.In an example, at least 90% halohydrin group can be cyclized to form nitrogen Azetidinium ion.Alternately, at least 95%, at least 97%, at least 98%, at least 98.5%, at least 99%, at least 99.5%th, at least 99.7%, at least 99.8% or at least 99.9% halohydrin group can be cyclized to be formed azetidine from Son.

For example, except those detailed above, the additional step in being processed using resin carrys out regulation composition Solids content.For example, resin combination can be by being converted into azetidine functionalization by halo alcohol functionalized polymers Polymer generates.After this step, pH polymer compositions can be adjusted so that the pH of resin combination can be from about 2 To about 4.5.Alternately, the pH of resin can be from about 2.2 to about 4.2, about 2.5 to about 4 or about 2.7 to about 3.7.Another In one example, when being measured at a temperature of about 25 DEG C, the pH of polymer composition can be adjusted to from low about 2, about 2.1, About 2.2, about 2.3, about 2.4, about 2.5, about 2.6 or about 2.7 paramount about 3, about 3.2, about 3.4, about 3.6, about 2.8, about 4, about 4.2 Or about 4.5 pH.The solids content that composition can also be entered to be about to after the procedure of pH adjustment is adjusted to about 50% from about 10% The step of to form fortified resin.Alternately, the solids content of composition can be from about 15% regulation to about 40% or from about 20% is adjusted to about 30% to form fortified resin.In another example, fortified resin can contain with about 25% solid Amount.

Gained fortified resin can have the charge density higher than conventional resins.For example, fortified resin can have about 2 to about The charge density of 4mEq/g solids.Alternately, fortified resin can have from about 2.25 to about 3.5mEq/g solids, about 2.3 To about 3.35mEq/g solids, about 2.4 to about 3.2mEq/g solids or about 2.5 to the charge density of about 3.0mEq/g solids.

Gained fortified resin can also have from the azetidinium ions and amine in the fortified resin of about 0.4 to about 2.3 The ratio of residue, it is abbreviated as " Azet ".Azet ratios can also be from about 0.5 to about 1.9, about 0.6 to about 1.6 or about 0.7 to About 1.3.In another example, the ratio of the azetidinium ions in resin and secondary amine moieties can be from about 0.4 to about 1.Azet ratios can utilize the methylene of sour residue in quantitative mesomethylene carbons and main chain of the 13C NMR by comparing azetidine Base determines.

In another example, fortified resin can have from about 0.02 × 10⁶To about 3.0 × 10⁶Mw molecular weight.Can Alternatively, resin can have from about 0.05 × 10⁶To about 2.5 × 10⁶, about 0.1 × 10⁶To about 2.0 × 10⁶, about 0.5 × 10⁶ To about 1.5 × 10⁶Or about 1 × 10⁶To about 1.0 × 10⁶Mw molecular weight.In another example, resin can have from about 0.05×10⁶To about 1.7 × 10⁶Mw molecular weight.Mw molecular weight can also be from about 0.6 × 10⁶To about 1.6 × 10⁶, about 0.7 ×10⁶To about 1.5 × 10⁶, about 0.8 × 10⁶To about 1.3 × 10⁶Or about 0.9 × 10⁶To about 1.1 × 10⁶。

Fortified resin can have the azetidine equivalent from about 1,600 to about 3,800, and it is defined as the degree of polymerization and is multiplied by Azet ratios or (degree of polymerization) x (Azet).Alternately, azetidine equivalent can be from about 1,800 to about 3,500 or about 2,000 to about 2,900.

Fortified resin can also have the various combinations of disclosed property.For example, fortified resin can show or have Charge density, Azet ratios, Mw molecular weight, azetidine equivalent, 1,3-DCP contents, cyclisation form azetidinium ions Halohydrin group etc. disclosed characteristic at least two, at least three, at least four or at least five.For example, strengthen Resin can show or with least two, at least three, at least four in following characteristics or whole five：(a) about 2.25 to about 3.5mEq/g solids charge density；(b) ratio of azetidinium ions and amide residues is in fortified resin About 0.7 to about 0.9；(c) about 0.05 × 10⁶To about 1.5 × 10⁶Mw molecular weight；(d) from the azepine of about 1,800 to about 3,500 Cyclobutane equivalent；When solids content be about 25% (e), the chloro- 2- propyl alcohol (1,3- of 1,3- bis- less than about 10,000ppm DCP) content.

Compared with traditional wet-strength resins system

As described in prepared by traditional wet-strength resins, when carrying out at room temperature, three key reactions in the conventional method (i.e. chloropharin side base forms (open loop), cyclisation forms azetidinium ions group (cationization) and crosslinking (intermolecular alkyl Change)) relative speed be respectively about 140:4:1.Therefore, using about 1:The epichlorohydrin and secondary amine of 1 mol ratio, by epichlorohydrin epoxy The ring-opening reaction of secondary amine forms chloropharin side base very fast in compound and prepolymer.Then chloropharin group is will be relatively slowly cyclized shape Into cationic nitrogen azetidine group.Even more slowly crosslink, such as carry out in the following manner：1) such as chloropharin side The tertiary amine of base reacts with azetidine moiety；And/or 2) tertiary amine and the intermolecular alkylation of chloropharin side base.Therefore, reacting Cross-linking stage in scheme, it is substantially absent from remaining secondary amine group.Crosslinking causes molecular weight to increase, and this is in resin viscosity Showed in increase.

In order to keep the actual utility of most short reaction circulation time, manufacturing process can be entered under high temperature and High Concentration Situation OK, the reaction rate wherein between intramolecular cyclization and crosslinking becomes have competitiveness.Therefore, run into conventional fabrication processes A problem be that cross-linking reaction speed becomes sufficiently fast so as to be that cost is issued to required forming azetidinium ions group Viscosity terminal (molecular weight).If reaction is allowed to continue to exceed required viscosity terminal to produce higher levels of azetidin Groups, then reactant mixture gelation and solid matter may be formed.

Because both high azetidine group content and HMW are imitated available for the maximum wet strength of PAE resin Rate, it is desirable that making the formation of azetidine group and crosslinking maximize without making product gel or providing during storage The product of gelation.These conditions, plus the requirement to high solid to minimize cost of transportation, limit to form high-efficiency wet The many aspects of intensity resin product.

On the contrary, the fortified resin and technique that are discussed herein and describe are at least partially through the higher azetidine of offer Ion concentration, the reactive functionalization of additional levels, increased molecular weight and extraordinary storage stability are asked to solve this Topic.When being applied for paper, cardboard, paper handkerchief and towel, fortified resin provides to be in progress relative to the improved wet tensile of current techniques.

The comparison of wet-strength resins performance and standard available wet-strength resins is provided in example and table.It has detected according to this The wet-strength resins performance of the open resin prepared, and with includingSeries plastics (Georgia-Pacific) and(Ashland) the standard available wet-strength resins product of resin is compared.Resin sheet is compared in the following table Two kinds of properties of body and the performance of the resin for assigning wet strength.Data illustrate (table 1) compared with conventional resins, disclosed Significantly improving for resin properties, such as the ratio of charge density increase, azetidinium ions and amide residues are observed in resin Example is higher, molecular weight is higher, azetidine equivalent is higher and by-product contamination thing is lower.

According on the other hand, there is provided a kind of fortified resin for being used to strengthen the wet strength of paper.For prepare resin or The method of resin combination can include making polyamine react with symmetrical crosslinking agent to produce partial cross-linked polyamine.Can be by table halogen It is added to for alcohol in partial cross-linked polyamine to obtain halo alcohol functionalized polymers.Halo alcohol functionalized polymers can be cyclized To form the resin with azetidine moiety.

When polyamine (polyamine prepolymer) is selected from Polyamide amine prepolymer, the disclosure further aspect provides one Kind be used for strengthen paper intensity (such as wet strength) resin, wherein resin include with derived from symmetrical crosslinking agent in function The partial cross-linked polyamide-based amine polymer of bridging and there are azetidinium ions.For preparing resin or resin combination Method can include making Polyamide amine (PAA) prepolymer with secondary amine group with deficiency with secondary amine reactivity part The reaction of symmetrical crosslinking agent, to provide partial cross-linked Polyamide amine prepolymer, it is remained a part of (such as most of) The secondary amine group being present in Polyamide amine prepolymer.If desired, Polyamide amine prepolymer can be crosslinked with symmetrical Before, during or after agent reaction, reacted with the simple function modifying agent comprising a secondary amine reactivity part of deficiency.Part The polyamidoamines amine prepolymer of crosslinking can be reacted with epihalohydrin to provide halo alcohol functionalized polymers.Resin combination can It is enough to be cyclized at least a portion halohydrin group to form azetidinium ions by being subjected to halo alcohol functionalized polymers Condition and formed.

Any paper strengthened using fortified resin is also an aspect of this disclosure and provided in the text.In addition, processing paper The fiber of paper can be manufactured using dried resin solids treatment to assign the technique of wet strength, wherein resin is the disclosure In any resin.For example, the technique can be using the fiber based on cationic thermosetting resin or resin combination Dry weight from about 0.05 weight % to about 2 weight % dried resin solids treatment manufacturing the fiber of paper, wherein resin or tree Oil/fat composition constructed according to the present disclosure.Processing paper may include using being based on cationic thermosetting resin with assigning the technique of wet strength The fiber dry weight of composition from about 0.01 weight % to about 2 weight % dried resin solids treatment manufacturing the fiber of paper. Alternately, the technique can use based on fiber dry weight from about 0.05 weight % to about 1.8 weight %, about 0.075 weight Measure % to about 1.6 weight % or about 0.1 weight % to about 1.5 weight % dried resin solid.Fiber can be paper pulp fiber.

Although every kind of resinous composition property disclosed herein is independently of each other properties and is described in detail, wish Any resin combination physical performance is hoped to occur together with any other resin properties in disclosed resin.Such as but not as Limitation, the disclosures of this paper properties include in can having the following properties that it is at least one, at least two, at least three, at least four It is individual or at least five composition：A) about 1.0 to about 4.0mEq/g solids charge density；B) azetidinium ions in resin Ratio with amide residues is from about 0.5 to about 0.9；C) from about 0.05 × 10⁶To about 3.0 × 10⁶Molecular weight；D) from about 1, The azetidine equivalent of 800 to about 3,500；And e) when solids content is about 25%, 1, the 3- bis- less than about 10,000ppm Chloro- 2- propyl alcohol (1,3-DCP) content.

In order to more clearly define terms used herein, there is provided it is defined below, unless otherwise stated, these are defined Suitable for the disclosure, as long as definition will not make it that any claim that this definition is applied is indefinite or invalid, for example, not observing The traditional rule of chemical valence.If having used term in the disclosure, but it is not specifically defined, then can applies herein The IUPAC technical terms of chemistry collect, the definition of second edition (1997), if this definition not with any other disclosure for applying herein or fixed Justice conflict or any claim for applying this definition are indefinite or invalid.Any file being just incorporated herein by reference Any definition for there is provided or using with provided herein is definition or for use conflicts, it then follows provided herein is definition or use.

Although composition and method are described in a manner of the various components of "comprising" or step, composition and method " substantially it can be made up of various components or step " or " being made up of various components or step ".

Except as otherwise noted, otherwise according to appropriate Practical in Chemistry, not specified any carbon-containing group of carbon number purpose can With 1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19,20,21,22,23,24,25,26,27, 28th, any scope or range combinations between 29 or 30 carbon atoms or these values.For example, except as otherwise noted, it is otherwise any Carbon-containing group can have from 1 to 30 carbon atom, from 1 to 25 carbon atom, from 1 to 20 carbon atom, from 1 to 15 carbon original Son, from 1 to 10 carbon atom or from 1 to 5 carbon atom etc..In addition it is possible to use other identifiers or limiting term and indicating Specified substituent, specific region be chemical and/or stereochemical existence or non-existence or the understructure of branch or depositing for main chain Or be not present.

Term " substituted " is when for describing group, such as when mentioning the substitution analog of special groups, to retouch Any non-hydrogen partial of the hydrogen substituted in form in the group is stated, is nonrestrictive.But applicant has the power to restrict and appointed What group, for example, limit the scope of any claim, to illustrate previous disclosure that applicant may be unaware that.Group is at this " unsubstituted " can also be referred to as in text or by equivalent term, such as " non-substituted ", it refers to wherein non-hydrogen partial The original group of hydrogen in the group is not substituted." substituted " to nonrestrictive, including pointed by those skilled in the art simultaneously The inorganic substituent or organic substituent of understanding.

Term " alkyl " as used herein is generic term, and it refers to by removing one or more hydrogen atoms from alkane (according to the needs of special groups) and formed group.Therefore, " alkyl " is included as defined in IUPAC by formal from alkane The definition for the univalent perssad for removing a hydrogen atom and being formed, but also include when context needs or allows, such as pass through shape Two hydrogen atoms are removed from alkane and form " alkane diyl " (two hydrogen atoms come from a carbon atom or a hydrogen atom in formula The carbon atom different from two), as long as the usual rule of applied chemistry valency.Unless otherwise stated, alkyl can be with It is substituted or unsubstituted group, can is non-annularity or the group of ring-type, and/or can be straight or branched.

Term " cycloalkyl " as used herein is generic term, and it refers to by removing one or more hydrogen from cycloalkane Atom (according to the needs of special groups) and formed group.Therefore, " cycloalkyl " is included as defined in IUPAC by from cycloalkanes The definition for the univalent perssad that hydrocarbon removes a hydrogen atom in form and formed, but also include when context needs or allows, example Such as by remove two hydrogen atoms from alkane in form formed " cycloalkanes diyl " (two hydrogen atoms from a carbon atom or One hydrogen atom is from two different carbon atoms), as long as the usual rule of applied chemistry valency.Unless otherwise indicated, it is no Then alkyl can be substituted or unsubstituted group, can be non-annularity or the group of ring-type, and/or can be straight or branched 's.When removing divided by being formed " cycloalkyl " group from cycloalkane on two hydrogen forms, two hydrogen atoms can from identical ring carbon, Two different ring carbons, or a ring carbon and one are removed on the carbon atom form of ring carbon.

" aryl " refers to by removing one or more hydrogen atoms (according to specific base from aromatic compounds (particularly aromatic hydrocarbons) The needs and wherein at least one of group are aromatics ring carbon atoms) and the group of formation.Therefore, " aryl " is included by from aromatic hydrocarbons shape The univalent perssad for removing a hydrogen atom in formula and being formed, but also include for example removing two hydrogen atom (its in form from aromatic hydrocarbons In it is at least one be aromatic hydrocarbon ring carbon) it is and caused " fragrant diyl ".Therefore, aromatic compounds is containing following Huckel (4n+2) Rule and the compound for containing the cyclic conjugated hydrocarbon of (4n+2) pi-electron, wherein n is the integer from 1 to about 5.Therefore, unless otherwise Illustrate, otherwise aromatic compounds and therefore " aryl " can be monocyclic or polycyclic.

" heteroaryl " refers to by removing one or more hydrogen atoms (according to the needs of special groups from heteroaromatics It is aromatic ring carbon or hetero atom with wherein at least one) and the group of formation.Therefore, one or more hydrogen atoms can be former from ring carbon Son and/or heteroaromatic rings or loop system hetero atom remove.Therefore, " heteroaryl " group or part include " heteroaryl diyl ", and it is logical Cross from heteroaryl hydrocarbon compound and remove two hydrogen atoms in form and produce, wherein at least one can be heteroaryl hydrocarbon ring or loop system Carbon atom.Therefore, in " heteroaryl diyl ", at least one hydrogen removes from heteroaryl hydrocarbon ring or loop system carbon atom, and another hydrogen Atom can remove from any other carbon atom, including such as heteroaryl hydrocarbon ring or loop system carbon atom or non-heteroaryl hydrocarbon ring or ring system System atom.

" acid amides " group or part refer to by from the amide compound including organic amide compound remove one or Multiple hydrogen atoms (according to the needs of special groups) and formed group.Therefore, one or more hydrogen atoms can from carboxyl carbon, Amide nitrogen, any organic moiety being bonded with carboxyl carbon or amide nitrogen or the organic moiety with carboxyl bond with carbon, and and acid amides The organic moiety of nitrogen bonding removes.Generally, for example, when amide group connects the amine in polyamines, " acid amides " group or part are logical Cross from each in two organic groups (one with carboxylic-bond and another is bonded with amide nitrogen) and remove one in form Hydrogen atom and produce.The term can be used for any amide moieties, either the organic group of acid amides or aliphatic series or aromatics.

Except as otherwise noted, otherwise various the substituted analogs or form derivative of these any groups can also be disclosed Use, in this case, analog or form derivative are not limited to the number of substituent or specific regional chemistry.Example Such as, term " hydroxyalkyl " refers to remove one or more hydrogen atoms in form by the moieties of the alkane substituted from hydroxyl (according to the needs of special groups) and formed group.The alkane of hydroxyl substitution can include one or more hydroxyl substituents. Therefore, " hydroxyalkyl " group is included for example when context needs or allows, by being removed in form from " hydroxyalkyl " alkane Two hydrogen atoms (two hydrogen atoms are from a carbon atom or a hydrogen atom from two different carbon atoms) and formed " alkane diyl " group of hydroxyl substitution, as long as the usual rule of applied chemistry valency.As for shown in alkyl, unless otherwise saying Bright, otherwise alkyl can be substituted or unsubstituted group, can be non-annularity or the group of ring-type, and/or can be straight chain Or side chain.

Shown in scheme 1 using adipic acid and DETA and epichlorohydrin synthetic standards PAE wet-strength resins.In scheme 2 In show one or more realities that the basis using symmetrical crosslinking agent methylene-bisacrylamide (MBA) is discussed herein and describe Apply the resin of example.

¹³Azetidine ratio (Azet ratios) in C NMR measure wet-strength resins

Azetidine ratio or " Azet " ratio are to include the polymer segment and polymer chain of azetidinium ions The ratio of section sum.Single polymer segment is by derived from two acid molecule (such as adipic acid) and a three amine molecule (examples Such as diethylenetriamines or DETA) condensation part definition, it is as follows.

Azetidinium ions ratio using 22.5 seconds relaxation time, 15000Hz spectrum width (240ppm) and from 320 to 1024 scanning passes through quantitative (multi channel heteronuclear decoupling)¹³C NMR spectras determine.Pass through azetidinium ions and polymerization The integration of methylene peak in the inside carbon of the adipic acid part of thing measures.Adipic acid part is considered as polymer segment Sum.Therefore, when preparing polymer using adipic acid, azetidine ratio determines according to following formula：

Azetidinium ions ratio (Azet ratios)=A (azet)/A (adip), wherein,

A (azet) is the integral area of the methylene from azetidinium ions；It is to come from adipic acid portion with A (adip) Divide the integral area of the methylene of (total polymer segment).This method is applicable to any resin disclosed herein.Therefore, for Polymer based on adipic acid, the azetidinium ions peak at 74ppm and the main chain methylene peak at 25ppm are integrated, and Methylene peak at 25ppm is normalized to 1.For the polymer based on glutaric acid, by the azetidinium ions at 74ppm Main chain methylene peak integration at peak and 22ppm, and the methylene peak at 22ppm is normalized to 1.

The charge density of wet-strength resins

Using M ü tek (Muetek) PCD-03 particle chargings detectors and titrator, measurement has about 10% to about as follows The charge density of the cationic polyamido amine of 50% typical non-volatile content-epichlorohydrin (PAE) wet-strength resins.Electric charge Density by using the weak solution of the polyanion solution titrimetry polycation resin of polyvinyl sulfate (PVSK) stream Streaming current potential determines.The non-volatile content of pre- measure PAE resin, and be single with milliequivalent (+)/gram solid (meq+/g) Position report charge density.

In the presence of Van der Waals force, polycation resin is preferentially adsorbed on test pond and its swings the table of discharge capacity piston Face, and when the liquid stream that the diffusion cloud of counter ion is tested in pond is cut off from cationic colloidal, cause so-called flowing electricity Stream.Electrode measurement this streaming current tested in pool wall.PAE resin is titrated with PVSK, until PAE resin reaches point of zero electric charge, And initial resin electric charge is calculated by titrant consumption amount.Streaming current is used for the cation electrodeposition that every gram of hard resin is calculated as below The milliequivalent number (meq+/g) of lotus：

The preparation of sheet material

As shown in table 2,3 and 4, the paper pulp raw material for handmade paper work is unique for each research.Resin with Lb/ton pulp solids shown in table are added to the dilution stock consistency (thick raw material %) shown in respective form, it is allowed to 2 minutes Incorporation time.The raw material of processing is poured into the Noble＆Wood write by hands for the water (pH value 7.0) being pre-adjusted containing pH immediately In the head box of paper machine.The base of target sheet material is 30lb/3000ft again².By every wet-sheet by being fully loaded with wet press twice, so It is placed on afterwards on 105 DEG C of drum dryers of no blotter 1 minute.All handmade papers enter in 105 DEG C of forced ventilation baking oven One step solidifies 10 minutes.Before testing, handmade paper sample is continued 24 under constant humidity (50%) and steady temperature (73 ℉) Hour.

Stretching measurement

Dry tensile and wet tensile (test sample is immersed in distilled water at 23.0 ± 0.2 DEG C) are tested to measure improved paper Dry and wet tensile strength character.Report the wet and dry breaking length (wet BL and dry BL) of dry and wet tensile, unit kM/m.Dry drawing Stretch measuring method and refer to TAPPI test method T494om-01 (September comes into force on the 5th within 2001).Wet tensile measuring method refers to TAPPI test method T456om-03 (on May 13rd, 2003 comes into force).

% is wet/dry tensile (%W/D stretchings)

% is wet/and dry tensile measured with the percentage of wet and dry stretching, i.e., and %W/D BL (breaking length) are (wet tensiles Breaking length)/(dry tensile breaking length) × 100.

Wet and dry tear

Dry tear measuring method refers to TAPPI test method T 414-om-04 (on May 3rd, 2004, issue came into force).By The wet tear measurement of TAPPI test method T 414-om-04 (on May 3rd, 2004, issue came into force) measure.

Example

Following instance is provided to illustrate the various embodiments of the disclosure and claims.Unless otherwise stated, examination Agent obtains from commercial source.Analysis below method is used to characterize resin.

The Polyamide amine prepolymer I of example 1 preparation

With the glass reactor at the top of 5 necks equipped with stainless steel agitating shaft, reflux condenser, temp probe and deep fat Bath.500.5 grams of DETA (diethylenetriamines) are added in reactor.Agitator is opened, under agitation after 45 minutes by 730 G of adipic acid is slowly added in reactor.Present invention temperature, which is added, in adipic acid is increased to 145 DEG C from 25 DEG C.Adipic acid adds After the completion of, reactor is immersed and is heated in 160 DEG C of hot oil bath.At 150 DEG C, reactant mixture starts to flow back.Will backflow Condenser is reconfigured to distill, and distillation is collected in single receiver.With interval sampling reaction mixing in 30 minutes Thing.Each samples with water is diluted to 45% solid, utilizes Brookfield viscosity meter viscosity.When sample reaches 290cP, Distiller condenser is reconfigured to flow back.Water is slowly added in reactant mixture to dilute and cool down by reflux condenser Reactant.Add water to obtain 45% final solid.Viscosity is 290cP.

The Polyamide amine prepolymer II of example 2 preparation

With the glass reactor at the top of 5 necks equipped with stainless steel agitating shaft, reflux condenser, temp probe and deep fat Bath.1574.5 grams of DBE-5 (dimethyl glutarate or dibasic ester) are added in reactor.Turn on agitator simultaneously under agitation will 1038.9 grams of DETA are added in reactor.Reactor is immersed and is heated in 100 DEG C of hot oil bath.At 90 DEG C, reaction mixing Thing starts to flow back.Reflux condenser is reconfigured to distill, and distillation is collected in single receiver.With 30 minutes Interval sampling reactant mixture.Each samples with water is diluted to 45% solid, and with Brookfield viscosity meter viscosity.When When sample reaches 220cP, distiller condenser is reconfigured to flow back.Water is slowly added to by reaction mixing by reflux condenser To dilute and cool down reactant in thing.Water is added to obtain 45% final solid.Viscosity is 220cP.

The preparation of the wet-strength resins of example 3

Step 1. have glass reactor at the top of 5 necks equipped with glass stir shaft and Teflon oars, isobaric addition funnel, Temperature and pH probes, stainless steel cooling coil, sample valve and heating mantle.445.64 grams of Polyamide amines from example 2 are pre- Polymers II is added in reactor.5.25 grams of water are added, start agitator.Reactant mixture is heated to 35 DEG C, adds 2.028 grams N, N- methylene-bis-acrylamide (Pfaltz＆Bauer, Inc.).Reactant mixture is heated to 60 DEG C and at this temperature Kept for 4 hours.The viscosity of reactant mixture increases to 384cP (Brookfield-SSA).Intermediate (partial cross-linked) pre-polymerization Thing mixture uses in the situ of following steps 2.

Step 2. adjusts the reaction temperature of the intermediate prepolymer mixture from step 1 to 25 DEG C, and adds 88.46 Gram water.Then reaction temperature is adjusted to 21 DEG C, and 121.21 grams of epichlorohydrins was added in 75 minutes.The reactant mixture is set to exist 25 DEG C are warming up in 45 minutes, and adds 446.27 grams of water.The reactant mixture is heated to 45 DEG C, and heated after 2 hours To 55 DEG C.After about 4 hours, the mixture of formic acid and sulfuric acid is added to adjust pH to 2.87.(generally, it can use any organic Acid, inorganic acid or its combination regulation pH, such as acetic acid, formic acid, hydrochloric acid, phosphoric acid, sulfuric acid or its any combinations).Then will reaction Mixture is cooled to 25 DEG C, adds water and adjusts solid to 25.0%.The viscosity of gained wet-strength resins is 187cP.

The preparation of the wet-strength resins of example 4

Step 1. have glass reactor at the top of 5 necks equipped with glass stir shaft and Teflon oars, isobaric addition funnel, Temperature and pH probes, stainless steel cooling coil, sample valve and heating mantle.1000.00 grams of Polyamide amines from example 1 are pre- Polymers I is added in reactor.Start agitator and prepolymer is heated to 40 DEG C.It is slowly added to N, N- methylene-bis--acryloyl Amine 15.16 grams (Pfaltz＆Bauer, Inc), while reactant mixture is heated to 60 DEG C.Then by reactant mixture at 60 DEG C It is lower to be kept for about 2 hours, and viscosity increases to 4,630cP (Brookfield-SSA), and now viscosity increase stops.It will react cold But to 25 DEG C.Intermediate (partial cross-linked) prepolymer is separated and stored.

Step 2. adds intermediate (partial cross-linked) prepolymer of 366.04 grams of above-mentioned steps 1 matches somebody with somebody as described in step 1 In the reactor put.Reaction temperature is adjusted to 25 DEG C, and adds 120.13 grams of water.The viscosity of reactant mixture is 837cP. At 25 DEG C, 77.89 grams of epichlorohydrins are added in the partial cross-linked prepolymer of intermediate in 90 minutes.428.19 grams of water are added In reactant mixture.Reaction is set to be kept for 18 hours at 25 DEG C, while periodically sampling carries out 13C NMR analyses.During this period, instead Viscosity is answered to increase to 319cP (Brookfield-SSA) from 18cP.The reaction is with dense sulfuric acid treatment so that pH is adjusted to 2.94.Will Reactant mixture is adjusted to 25.0% solid, viscosity 335cP.

The preparation of the wet-strength resins of example 5

Step 1. have glass reactor at the top of 5 necks equipped with glass stir shaft and Teflon oars, isobaric addition funnel, Temperature and pH probes, stainless steel cooling coil, sample valve and heating mantle.449.10 grams of Polyamide amines from example 2 are pre- Polymers II is added in reactor.Start agitator, reactant mixture is heated to 30 DEG C, 6.92 grams poly- (third were added in 1 hour Glycol) diglycidyl ether (Polystar).Reactant mixture is kept for 1 hour at 30 DEG C, is then heated to 60 DEG C, now Viscosity is 416cP.Reactant mixture is heated about 4 hours at 60 DEG C, viscosity increases to 542cP (Brookfield-SSA). Intermediate crosslinkable prepolymer uses in subsequent step 2 situ.

Step 2. adjusts the reaction temperature of the intermediate pre-polymer mixture from step 1 to 25 DEG C, and adds 80.10 Gram water.118.79 grams of epichlorohydrins are added in reactor in 75 minutes.Reaction was warming up to 30 DEG C in 45 minutes, and add 431.35 grams of water.Reaction is warming up to 45 DEG C in 45 minutes, and is heated to 50 DEG C after 2 hours.After about 3.5 hours, reaction Viscosity be about 320cP (Gardner-Holdt bubbler tubes), then add the mixture of formic acid and sulfuric acid with adjust pH to 3.00.Reactant mixture is cooled to 25 DEG C, and adds water to adjust solid to 25.0%.The viscosity of gained wet-strength resins is 219cP。

The preparation of the handmade paper of example 6

The comparison of wet-strength resins and standard available wet-strength resins is provided in example and tables of data.Each tables of data The middle raw material used of instruction, and report raw material freedom (CSF).With shown speed (1b resins/ton pulp solids) Resin is added in thick raw material, it is allowed to the incorporation time of 2 minutes.The raw material after processing is poured into immediately and is pre-adjusted containing pH Water Noble＆Wood handmade paper machines head box in.

Target sheet material base is focused in each group of data with lb/ft²Represent.Each wet-sheet by fully loaded wet press twice, It is then placed within 105 DEG C of drum dryers of no blotter 1 minute.Forced ventilation baking oven of all handmade papers at 105 DEG C In further solidification 10 minutes.Before test, by handmade paper sample under constant humidity (50%) and steady temperature (73 ℉) Continue 24 hours.Any additional conditions are reported in table.Before test, by handmade paper sample in constant humidity (50%) and perseverance Continue 24 hours under constant temperature degree (73 ℉).

With the ratio (lb/ton) of the pulp solids shown in each tables of data by composition resin be added to thick slurry material (referring to Form), it is allowed to the incorporation time of 2 minutes.The raw material of processing is poured into the water (pH value 7.0) that is pre-adjusted containing pH immediately In the head box of Noble＆Wood handmade paper machines.Target sheet material base, which is focused in each form, to be pointed out.Every wet-sheet is passed through full Carry wet press twice, be then placed on 105 DEG C of drum dryers of no blotter 1 minute.All handmade papers are strong at 105 DEG C Further solidify 3 minutes in ventilated drying oven processed.Before testing, by handmade paper sample in constant humidity (50%) and steady temperature Continue 24 hours under (73 ℉).

The evaluation of the composition property of example 7 and performance

The comparison of wet-strength resins performance and standard available wet-strength resins is provided in the following table.It has detected according to this public affairs Open the wet-strength resins performance of the resin of preparation, and with includingSeries plastics (Georgia-Pacific) and(Ashland) the standard available wet-strength resins product of resin is compared.Resin sheet is compared in the following table Two kinds of properties of body and the performance of the resin for assigning wet strength.

Table 1 illustrates compared with commercial resins, and significant improved properties are shown according to wet-strength resins prepared by the disclosure. For example, under suitable solids content, compared with conventional resins, the resin of example 3 has significantly higher charge density, azacyclo- The ratio of butane ion and amide residues, molecular weight, azetidine equivalent and other properties.In addition, it is not required in gained resin Chloro- 2- propyl alcohol (1,3-DCP) contents of 1,3- bis- wanted substantially reduce.

Table 1 is compared with commercial resins, the property of wet-strength resins^A

^AAbbreviation is as follows：

Solid is total solid or nonvolatile matter in resin material, including polymer and any additive.

Electric charge is with the charge density that every gram of solid of milliequivalent (meq/g) is unit, by using Muetek burette tests Burette test measure.

Azet is azetidinium ions and amide residues in the wet-strength resins measured by quantitative 13C NMR spectras Ratio.

Mw is weight average molecular weight.

Azet Eq Wt are that the degree of polymerization is multiplied by Azet ratios, or (degree of polymerization) × (Azet).

DCP@25% are the epichlorohydrin hydrolysising by-product 1,3- dichlorohydrins (DCP) being retained under 25% solid in resin Concentration.

Table 2 illustrates that the wet breaking length of premium grade weight matter towel changes when with according to the resin treatment of the disclosure Enter.The comparison of the same nature obtained using conventional resins is provided with the data measured under different administration rate.Use such as this public affairs The resin for opening middle preparation observes the substantial improvements of property.

Table 2 is under different administration rate, compared with commercial resins, the performance of wet-strength resins^A

^ACondition：Premium grade (bleaching is original) heavyweight towel, Noble＆Wood sheet formers, target Sheet basis weight 28lb/3000sq ft, BSWK, pH 7.54, thick raw material 2.31%, raw material freedom 584CSF, CMC 2lb/ton, solidification 5min/105℃。

Table 3 equally illustrates to work as uses root under different rate of application (5,10 and 15 pounds of composition resins of pulp solids per ton) According to the disclosure resin treatment when the improvement of the wet breaking length of heavy towel that circulates.The phase obtained using conventional resins is provided Connatural comparison.In each case, the substantial improvements of the performance using disclosed wet-strength resins are illustrated.

Table 3 is under different administration rate, compared with commercial resins, the performance characteristics of wet-strength resins^A

^ACondition：The heavyweight towel of 100% circulation；Noble＆Wood sheet formers, 28lb/3000sq ft；pH 7.5；Thick raw material 1.50%, 475CSF, the ℉ of drier 230, solidify 5 minutes/105 DEG C.

Similarly, table 4 is illustrated compared with more conventional resin material, in different administration rate (pulp solids 4 per ton, 6 and 8 pounds of composition resins) under the breaking length for not bleaching SW brown paper wet tensile and % it is wet/improvement of dry tensile.Every In the case of kind, the performance improvement for using disclosed wet-strength resins is all observed.Also report and measure using the resin specified Wet tear, and again, under every kind of rate of application, illustrate the improvement of the performance using disclosed wet-strength resins.

Table 4 is under different administration rate, compared with commercial resins, the performance characteristics of wet-strength resins^A

^ACondition：100% unbleached SW brown paper, Noble＆Wood sheet formers, 83lb/3000sq ft；PH= 6.97, thick raw material 2.51%, 714CSF, 13lb/ton alum, by 4 times on the ℉ of drier 230, solidify 5 minutes/105 DEG C.

Embodiment of the disclosure is further to any one or more in paragraphs below：

1. a kind of technique for being used to prepare resin, including：A) polyamine is made to be reacted with symmetrical crosslinking agent to be made partial cross-linked Polyamine；B) epihalohydrin is added in the partial cross-linked polyamine so that halo alcohol functionalized polymers are made；And c) ring Change the halo alcohol functionalized polymers to form the resin with azetidine moiety.

2. according to the technique described in paragraph 1, wherein the polyamine has the structure

Wherein R is alkyl, hydroxyalkyl, amine, acid amides, aryl, heteroaryl or cycloalkyl, and w is from 1 to about 10,000 Integer.

3. according to the technique described in paragraph 1, wherein the polyamine has about 2,000 to about 1,000,000 molecular weight.

4. according to the technique described in paragraph 3, wherein the polyamine has about 10,000 to about 200,000 molecular weight.

5. according to the technique described in paragraph 1, wherein the symmetrical crosslinking agent be selected from diacrylate, double (acrylamides), Diepoxide and poly- azetidine compounds.

6. according to the technique described in paragraph 1, wherein the symmetrical crosslinking agent is selected from：

Wherein R4 is (CH₂)_t, and wherein t is 1,2 or 3；

Wherein x is from 1 to about 100；

Wherein y is from 1 to about 100；

Wherein x'+y' is from 1 to about 100；

Wherein z is from 1 to about 100；

Wherein q/p ratios are From about 10 to about 1000；

Acrylate monomer, methacrylate monomers, olefinic monomer or diene monomers are with being selected from following azetidin The copolymer of alkane functionalized monomer：With and combinations thereof, wherein institute State azetidine functionalized monomer described in copolymer and the acrylate monomer, the methacrylate monomers, institute The fraction for stating olefinic monomer or the diene monomers is from about 0.1% to about 12%；And its any combinations.

7. according to the technique described in paragraph 1, wherein the symmetrical crosslinking agent is selected from N, N'- methylene-bis-acrylamides, It is N, N'- methylene-bis--Methacrylamide, PEG diglycidyl ether, poly- (propane diols) diglycidyl ether, poly- Glycol diacrylate, poly- azetidine compounds and its any combinations.

8. according to the technique described in paragraph 1, wherein the epihalohydrin is selected from epichlorohydrin, epibromohydrin and epiiodohydrin.

9. according to the technique described in paragraph 8, wherein the epihalohydrin is epichlorohydrin.

10. according to the technique described in paragraph 1, it further comprises：Before using the symmetrical crosslinking agent processing, period Or the polyamine is set to be reacted with simple function modifying agent afterwards.

11. according to the technique described in paragraph 10, wherein the simple function modifying agent is selected from neutral or cationic acrylate Compound, neutrality or cation acrylamide compound, acrylonitrile compound, monoepoxide or its combination.

12. according to the technique described in paragraph 10, wherein the simple function modifying agent is selected from alkyl acrylate, acryloyl Amine, alkyl acrylamide, dialkylacrylamides, acrylonitrile, 2- alkyl epoxies ethane, 2- (allyloxy alkyl) epoxy second Alkane, hydroxyalkyl acrylates, ω-(acryloxy)-alkyl trimethyl ammonium compounds, ω-(acrylamido)-alkyl front three Base ammonium compounds and its any combinations.

13. according to the technique described in paragraph 10, wherein the simple function modifying agent include it is following in it is at least one：Acrylic acid Methyl esters, alkyl acrylate, acrylamide, N methacrylamide, N, N- DMAAs, acrylonitrile, 2- methyl rings Oxidative ethane, 2- ethyls oxirane, 2- propyIoxiranes, 2- (allyloxy methyl) oxirane, acrylic acid 2- hydroxyl ethyl esters, Acrylic acid 2- (2- hydroxyl-oxethyls) ethyl ester, 2- (acryloxy)-N, N, N- trimethyl second ammonium, 3- (acryloxy)-N, N, N- trimethyl propyl- 1- ammoniums, 2- acrylamidos-N, N, N- trimethyl second ammonium, 3- acrylamidos-N, N, N- trimethyl propyl- 1- ammoniums and 1- isopropyls -3- (methacryloxy) -1- methyl azetidine chlorine.

14. according to the technique described in paragraph 1, wherein the ratio of azetidinium ions and secondary amine moieties is in the resin From about 0.4 to about 1.0.

15. according to the technique described in paragraph 1, wherein the concentration of 1,3- bis- chloro- 2- propyl alcohol (1,3-DCP) is less than about 15, 000ppm。

16. according to the technique described in paragraph 1, wherein adjusting the pH of the resin using acid.

17. according to the technique described in paragraph 16, wherein the acid is acetic acid, formic acid, hydrochloric acid, phosphoric acid, sulfuric acid, organic acid or Inorganic acid or its combination.

18. according to the technique described in paragraph 16, wherein the pH of the resin is adjusted to about pH 2.0 to about pH 4.5.

19. according to the technique described in paragraph 1, wherein the solids content of the resin is adjusted to about from about 10% 50%.

20. according to the technique described in paragraph 1, wherein the resin is close with about 1.0 to about 4.0mEq/g solids electric charge Degree.

21. according to the technique described in paragraph 1, wherein the resin has the azetidinium ions from about 0.5 to about 0.9 With the ratio of amide residues.

22. according to the technique described in paragraph 1, wherein the resin has from about 0.02 × 10⁶To about 3.0 × 10⁶Molecule Amount.

23. according to the technique described in paragraph 1, wherein the resin has the azetidine from about 1,800 to about 3,500 Equivalent.

24. according to the technique described in paragraph 1, wherein the resin has the chloro- 2- third of 1,3- bis- less than about 10,000ppm Alcohol (1,3-DCP) content.

25. one kind wraps resiniferous composition, wherein the resin including following technique by preparing：A) make polyamine with Symmetrical crosslinking agent reaction is with obtained partial cross-linked polyamine；B) epihalohydrin is added in the partial cross-linked polyamine to be made Halo alcohol functionalized polymers；And the halo alcohol functionalized polymers c) are cyclized to be formed with azetidine moiety The resin.

26. according to the composition described in paragraph 25, wherein the polyamine has the structure

Wherein R is alkyl, hydroxyalkyl, amine, acid amides, aryl, heteroaryl or cycloalkyl, and w is from 1 to about 10,000 Integer.

27. according to the composition described in paragraph 25, wherein the polyamine has about 2,000 to about 1,000,000 molecule Amount.

28. according to the composition described in paragraph 27, wherein the polyamine has about 10,000 to about 200,000 molecule Amount.

29. according to the composition described in paragraph 25, wherein the symmetrical crosslinking agent is selected from diacrylate, double (acryloyls Amine), diepoxide and poly- azetidine compounds.

30. according to the composition described in paragraph 25, wherein the symmetrical crosslinking agent is selected from：

Wherein R4 is (CH₂)_t, and wherein t is 1,2 or 3；

Wherein x is from 1 to about 100；

Wherein y is from 1 to about 100；

Wherein x'+y' is from 1 to about 100；

Wherein z is from 1 to about 100；

Wherein q/p ratios are From about 10 to about 1000；

Acrylate monomer, methacrylate monomers, olefinic monomer or diene monomers are with being selected from following azetidin The copolymer of alkane functionalized monomer：With and combinations thereof, wherein institute State azetidine functionalized monomer described in copolymer and the acrylate monomer, the methacrylate monomers, institute The fraction for stating olefinic monomer or the diene monomers is from about 0.1% to about 12%；And its any combinations.

31. according to the composition described in paragraph 25, wherein the symmetrical crosslinking agent is selected from N, N'- methylene-bis--acryloyl Amine, N, N'- methylene-bis--Methacrylamide, PEG diglycidyl ether, poly- (propane diols) diglycidyl ether, Polyethyleneglycol diacrylate, poly- azetidine compounds and its any combinations.

32. according to the composition described in paragraph 25, wherein the epihalohydrin is selected from epichlorohydrin, epibromohydrin and epiiodohydrin.

33. according to the composition described in paragraph 32, wherein the epihalohydrin is epichlorohydrin.

34. according to the composition described in paragraph 25, wherein the technique further comprises：Utilizing the symmetrical crosslinking agent The polyamine is set to be reacted with simple function modifying agent before, during or after processing.

35. according to the composition described in paragraph 34, wherein the simple function modifying agent is selected from neutral or cation acrylic Ester compounds, neutrality or cation acrylamide compound, acrylonitrile compound, monoepoxide or its combination.

36. according to the composition described in paragraph 34, wherein the simple function modifying agent is selected from alkyl acrylate, acryloyl Amine, alkyl acrylamide, dialkylacrylamides, acrylonitrile, 2- alkyl epoxies ethane, 2- (allyloxy alkyl) epoxy second Alkane, hydroxyalkyl acrylates, ω-(acryloxy)-alkyl trimethyl ammonium compounds, ω-(acrylamido)-alkyl front three Base ammonium compounds and its any combinations.

37. according to the method described in paragraph 34, wherein the simple function modifying agent include it is following in it is at least one：Acrylic acid Methyl esters, alkyl acrylate, acrylamide, N methacrylamide, N, N- DMAAs, acrylonitrile, 2- methyl rings Oxidative ethane, 2- ethyls oxirane, 2- propyIoxiranes, 2- (allyloxy methyl) oxirane, acrylic acid 2- hydroxyl ethyl esters, Acrylic acid 2- (2- hydroxyl-oxethyls) ethyl ester, 2- (acryloxy)-N, N, N- trimethyl second ammonium, 3- (acryloxy)-N, N, N- trimethyl propyl- 1- ammoniums, 2- acrylamidos-N, N, N- trimethyl second ammonium, 3- acrylamidos-N, N, N- trimethyl propyl- 1- ammoniums and 1- isopropyls -3- (methacryloxy) -1- methyl azetidine chlorine.

38. according to the composition described in paragraph 25, wherein the ratio of azetidinium ions and secondary amine moieties in the resin Rate is about 0.4 to about 1.0.

39. according to the composition described in paragraph 25, wherein the concentration of 1,3- bis- chloro- 2- propyl alcohol (1,3-DCP) is less than about 15, 000ppm。

40. according to the composition described in paragraph 25, wherein adjusting the pH of the resin using acid.

41. according to the composition described in paragraph 40, wherein the acid is acetic acid, formic acid, hydrochloric acid, phosphoric acid, sulfuric acid, organic acid Or inorganic acid or its combination.

42. according to the composition described in paragraph 40, wherein the pH of the resin is adjusted to about pH 2.0 to about pH 4.5.

43. according to the composition described in paragraph 25, wherein by the solids content of the resin from about 10% adjust to About 50%.

44. according to the method described in paragraph 25, wherein the resin is close with about 1.0 to about 4.0mEq/g solids electric charge Degree.

A kind of 45. composition with least three following characteristics：A) about 1.0 to about 4.0mEq/g solids electric charge it is close Degree；B) ratio of azetidinium ions and amide residues is about 0.5 to about 0.9 in resin；C) about 0.1 × 10⁶To about 3.0 × 10⁶Molecular weight；D) the azetidine equivalent of about 1,800 to about 3,500；And e) it is less than when solids content is about 25% About 10,000ppm chloro- 2- propyl alcohol (1,3-DCP) contents of 1,3- bis-.

A kind of 46. paper that composition using either segment in 25-45 sections is strengthened.

47. a kind of processing paper, to assign the technique of wet strength, the technique is handled for making using resin combination The paper pulp fiber of papermaking, the resin combination pass through following preparation：A) polyamine is made to be reacted with symmetrical crosslinking agent so that part is made The polyamine of crosslinking；B) epihalohydrin is added in the partial cross-linked polyamine so that halo alcohol functionalized polymers are made；And C) the halo alcohol functionalized polymers cyclisation is made to form the resin with azetidine moiety.

48. a kind of fortified resin, comprising the polyamine partial cross-linked with bridging part and there are azetidinium ions, its Described in bridging part derived from including diisocyanate, 1,3- dialkyl group diazetidine -2,4- diketone, dianhydride, two acyls Base halogen, dienone, dialkyl group halogen or its any mixture function on symmetrical crosslinking agent.

49. a kind of be used to strengthen the method for paper, including make fiber with comprising the polyamine partial cross-linked with bridging part and Fortified resin contact with azetidinium ions, wherein the bridging part, which is derived from, includes diisocyanate, 1,3- bis- Alkyl diazetidine -2,4- diketone, dianhydride, diacyl halogen, dienone, dialkyl group halogen or its any mixture function on Symmetrical crosslinking agent.

50. a kind of method for preparing fortified resin, including：Polyamine is set to be reacted with symmetrical crosslinking agent in function to make Partial cross-linked polyamine is obtained, wherein symmetrical crosslinking agent includes diisocyanate, 1,3- dialkyl group diazacyclos in the function Butane -2,4- diketone, dianhydride, diacyl halogen, dienone, dialkyl group halogen or its any mixture；And make described partial cross-linked Polyamine and epihalohydrin react so that the fortified resin with azetidinium ions is made.

51. fortified resin or method according to either segment in paragraph 48 to 50, wherein symmetrically being handed in the function Connection agent includes diisocyanate.

52. fortified resin or method according to either segment in paragraph 48 to 51, wherein the diisocyanate is envelope The diisocyanate at end.

53. fortified resin or method according to either segment in paragraph 48 to 52, wherein symmetrically being handed in the function Connection agent includes the 1,3- dialkyl group diazetidine -2,4- diketone.

54. fortified resin or method according to either segment in paragraph 48 to 53, wherein symmetrically being handed in the function Connection agent includes the dianhydride.

55. fortified resin or method according to either segment in paragraph 48 to 54, wherein symmetrically being handed in the function Connection agent includes the diacyl halogen.

56. fortified resin or method according to either segment in paragraph 48 to 55, wherein symmetrically being handed in the function Connection agent includes the dienone.

57. fortified resin or method according to either segment in paragraph 48 to 56, wherein symmetrically being handed in the function Connection agent includes the dialkyl group halogen.

58. fortified resin or method according to either segment in paragraph 48 to 57, wherein symmetrically being handed in the function Join agent further comprising diacrylate compounds, double (acrylamide) compounds, diepoxide, poly- azetidine chemical combination Thing, N, N'- methylene-bis--Methacrylamide, poly- (aklylene glycol) diglycidyl ether or its any mixture.

59. fortified resin or method according to any one of paragraph 48 to 58, wherein the polyamine includes polyamide Base amine.

60. fortified resin or method according to either segment in paragraph 48 to 59, wherein the azetidinium ions By making epihalohydrin and being reacted with the partial cross-linked polyamine in the bridging part to be formed.

61. fortified resin or method according to any one of paragraph 48 to 60, wherein the fortified resin has 2.25mEq/g solids to 3.5mEq/g solids charge density.

62. fortified resin or method according to any one of paragraph 48 to 61, wherein the fortified resin has 2, 000 to 3,500 azetidine equivalent.

63. fortified resin or method according to either segment in paragraph 48 to 62, wherein the fortified resin has 900,000 to 1,700,000 weight average molecular weight.

64. fortified resin or method according to either segment in paragraph 48 to 63, wherein the fortified resin contain it is small In the chloro- 2- propyl alcohol of 10,000ppm 1,3- bis-.

65. fortified resin or method according to either segment in paragraph 48 to 60, wherein the fortified resin has 2.25mEq/g solids are to the charge density of 3.5mEq/g solids, 2,000 to 3,500 azetidine equivalent, 900.000 to 1,700,000 weight average molecular weight, and contain the chloro- 2- propyl alcohol of 1,3- bis- less than 10,000ppm.

66. fortified resin or method according to any one of paragraph 48-65, wherein being symmetrically crosslinked in the function Agent is further comprising diacrylate compounds, double (acrylamide) compounds, diepoxide, poly- azetidine chemical combination Thing, N, N'- methylene-bis--Methacrylamide, poly- (aklylene glycol) diglycidyl ether or its any mixture.

Some embodiments and feature are described using the set of number upper limit and set of number lower limit.It should be appreciated that Unless otherwise noted, the scope for including the combination of any two value, such as any lower value and any high value are otherwise wished Combination, the combination of any two lower value, and/or the combination of any two high value.Some lower limits, the upper limit and scope appear in In following one or more claims.All numerical value is indicated value " about " or " approximation ", and considers ability The experimental error and change that domain those of ordinary skill is expected.

Various terms have had already defined above.To a certain extent, the art that the above uses in the claims without definition Language, then should provide various equivalent modifications its widest definition for being assigned, such as an at least printed publication or award As power patent reflects.And all patents if applicable, quoted in the application, test program and other files It is fully incorporated herein by quoting, its degree and the application not contradiction, and for being had jurisdiction, such introducing is to be permitted Perhaps.

, can be in the feelings for the base region for not departing from the present invention although foregoing teachings are related to some illustrative embodiments The other and further embodiment of the present invention is designed under condition, and its scope is determined by following claims.

Claims (20)

1. a kind of fortified resin, comprising the polyamine partial cross-linked with bridging part and there are azetidinium ions, wherein institute State bridging part and include diisocyanate, 1,3- dialkyl group diazas derived from symmetrical crosslinking agent in function, the crosslinking agent Cyclobutane -2,4- diketone, dianhydride, diacyl halogen, dienone, dialkyl group halogen or its any mixture.

2. fortified resin according to claim 1, wherein symmetrical crosslinking agent further includes two propylene in the function Ester compound, double (acrylamide) compounds, diepoxide, poly- azetidine compounds, N, N'- methylene-bis--first Base acrylamide and poly- (aklylene glycol) diglycidyl ether or its any mixture.

3. fortified resin according to claim 1, wherein symmetrical crosslinking agent includes two isocyanic acid in the function Ester.

4. fortified resin according to claim 3, wherein the diisocyanate is the diisocyanate of end-blocking.

5. fortified resin according to claim 1, wherein symmetrical crosslinking agent includes 1, the 3- dioxanes in the function Base diazetidine -2,4- diketone.

6. fortified resin according to claim 1, wherein symmetrical crosslinking agent includes the dianhydride in the function.

7. fortified resin according to claim 1, wherein symmetrical crosslinking agent includes the diacyl halogen in the function.

8. fortified resin according to claim 1, wherein symmetrical crosslinking agent includes the dienone in the function.

9. fortified resin according to claim 1, wherein symmetrical crosslinking agent includes the dialkyl group halogen in the function.

10. fortified resin according to claim 1, wherein the polyamine includes Polyamide amine.

11. fortified resin according to claim 1, wherein the azetidinium ions by make epihalohydrin and with institute State the partial cross-linked polyamine reaction in bridging part and formed.

12. fortified resin according to claim 1, wherein the fortified resin has 2.25mEq/g solids to 3.5mEq/ The charge density of g solids.

13. fortified resin according to claim 1, wherein the fortified resin has 2,000 to 3,500 azetidin Alkane equivalent.

14. fortified resin according to claim 1, wherein the fortified resin has 900,000 to 1,700,000 weight Average molecular weight.

15. fortified resin according to claim 1, wherein the fortified resin contains 1, the 3- bis- less than 10,000ppm Chloro- 2- propyl alcohol.

16. fortified resin according to claim 1, wherein the fortified resin has 2.25mEq/g solids to 3.5mEq/ The charge density of g solids, 2,000 to 3,500 azetidine equivalent, 900,000 to 1,700,000 weight average molecular weight are simultaneously Contain the chloro- 2- propyl alcohol of 1,3- bis- less than 10,000ppm.

17. a kind of method for manufacturing fortified resin, including：

Symmetrical crosslinking agent in polyamine and function is set to react so that partial cross-linked polyamine is made, wherein symmetrically being handed in the function Join agent and include diisocyanate, 1,3- dialkyl group diazetidine -2,4- diketone, dianhydride, diacyl halogen, dienone, dioxane Base halogen or its any mixture；And

The partial cross-linked polyamine is set to be reacted with epihalohydrin so that the fortified resin with azetidinium ions is made.

18. according to the method for claim 17, wherein there is the fortified resin 2.25mEq/g solids to consolidate to 3.5mEq/g The charge density of body, 2,000 to 3,500 azetidine equivalent, 900,000 to 1,700,000 weight average molecular weight simultaneously contain There is the chloro- 2- propyl alcohol of 1,3- bis- less than 10,000ppm.

19. according to the method for claim 18, wherein symmetrical crosslinking agent further includes diacrylate in the function Ester compounds, double (acrylamide) compounds, diepoxide, poly- azetidine compounds, N, N'- methylene-bis--methyl Acrylamide, poly- (aklylene glycol) diglycidyl ether or its any mixture.

20. a kind of be used to strengthen the method for paper, including make fiber and comprising the polyamine partial cross-linked with bridging part and have The fortified resin contact of azetidinium ions, wherein the bridging part is derived from symmetrical crosslinking agent in function, the friendship Join agent and include diisocyanate, 1,3- dialkyl group diazetidine -2,4- diketone, dianhydride, diacyl halogen, dienone, dioxane Base halogen or its any mixture.