A guanidine salt polymer and its preparation method and use

Abstract

The present invention discloses a guanidine polymer and its preparation method and use. The guanidine polymer has a structure of R-NH-a-R'; wherein a includes at least one structural unit shown in the general formula (A); R and R' are each independently selected from hydrogen, a structural unit having one or more of the structures shown in (Formula 21) to (Formula 25), and R and R' are not hydrogen at the same time. The preparation method of the guanidine polymer includes: selecting at least one guanidine salt having a structure shown in the general formula (3) and at least one double-terminal amino diamine having a structure shown in the general formula (4) for condensation polymerization; and then performing the end-capping reaction with an end-capping agent. The guanidine polymer of the present invention has high end-capping reaction efficiency during the synthesis process and can be carried out under mild conditions; the production and product safety are both high, and the product quality of the grafted polymer produced subsequently is improved.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer compounds, in particular to a guanidine polymer and a preparation method and use thereof, and belongs to C08G 73 / 00 in the International Patent Classification Table. Background Art

[0002] Microorganisms are closely related to human life. Although most bacteria are beneficial to humans, a small number of pathogens and viruses have a significant negative impact on human daily life and even life. Therefore, vigorously developing antibacterial and antiviral anti-harmful microbial materials is of great significance to human public health and health.

[0003] It is known in the industry that guanidine polymers have excellent anti-harmful microbial functions and have been widely used in the fields of medical and health materials, biomaterials, and daily necessities. Peng Kaimei et al. (Acta Chimica Sinica, 2016, 74, 713-725) reviewed the research, application, and development trends of guanidine polymers at home and abroad, among which the application of guanidine polymers in the field of polymer materials is an important application direction.

[0004] Patent CN101982202 B discloses bonding guanidine polymers to the molecular chains of hydrogels to produce a highly safe hydrogel with anti-harmful microbial function; Patent CN103937003 B discloses preparing guanidine polymers into block copolymers with different structures to form a structure with selectivity of amphiphilicity or biocompatibility and strong anti-harmful microbial properties, and bonding them to general polyolefin molecular chains.

[0005] The guanidine polymer used in the above patent has amino groups at both ends of its molecular chain. In the reaction process with epoxy, isocyanate, carboxylic acid or anhydride, it shows multifunctional reaction characteristics. In this case, cross-linking reaction is very likely to occur, which seriously affects the processing performance, mechanical properties and resistance to harmful microorganisms of the final material. In this regard, patent CN106800652 B discloses a technology of using non-polar long-chain aliphatic monoamine structure to end-cap guanidine oligomers, and obtains It is a new type of guanidine oligomer with a capped structure, which can effectively reduce the cross-linking reaction when it reacts with the polymer.

[0006] However, due to the low reactivity of long-chain fatty amines and guanidine salt oligomers, the poor compatibility of fatty chains and guanidine salt polymers, the low efficiency of bonding and end-capping, a large amount of fatty amines that do not participate in the reaction will remain in the system and be difficult to separate, which will have an adverse effect on the preparation and later use performance of the anti-harmful microbial materials prepared by this method; moreover, fatty amines themselves have the disadvantages of high corrosiveness, high irritation, and high toxicity, which will bring great safety hazards during processing and use. Therefore, further research and innovation on the end-capping technology of guanidine salt polymers is needed. Summary of the invention

[0007] The purpose of the present invention is to overcome the above problems existing in the prior art and provide a guanidine polymer and a preparation method and use thereof.

[0008] The present invention adopts the following technical solutions to solve the above technical problems:

[0009] The present invention provides a guanidine polymer having a structure of R-NH-a-R';

[0010] Wherein, a comprises at least one structural unit represented by general formula (A), Y n - Selected from Cl - Br - 、HSO4 - 、HCO3 - 、H2PO4 - 、CH3COO - or CH3(CH2) 16 COO - ; R n A structural unit selected from one or more of the structures shown in (Formula 11), (Formula 12), (Formula 13), (Formula 14), (Formula 15), (Formula 16) and (Formula 17);

[0011]

[0012] Wherein, R and R' are each independently selected from hydrogen, the structural unit represented by (Formula 21), the structural unit represented by (Formula 22), the structural unit represented by (Formula 23), the structural unit represented by (Formula 24) or the structural unit represented by (Formula 25), and R and R' are not hydrogen at the same time;

[0013]

[0014] R3 is C4~C 12 Alkyl; R4 is C2~C4 alkylene; R5 is C2~C 12Alkyl, substituted or unsubstituted C5-C8 cycloalkyl, benzyl or phenethyl; R6 is p-toluenesulfonyl.

[0015] In the present invention, according to the conventional art, the R-NH- group in the guanidine polymer is connected to the Rn group in the structural unit represented by the general formula (A) at one end of a, and R' is connected to the terminal imino group in the structural unit represented by the general formula (A) at the other end of a.

[0016] In some embodiments, Y n - Preferably selected from Cl - 、HCO3 - 、H2PO4 - or CH3(CH2) 16 COO - .

[0017] In some embodiments, R n It is preferably selected from one or more structural units having the structure shown in (Formula 11), the structure shown in (Formula 13), the structure shown in (Formula 14) and the structure shown in (Formula 16).

[0018] In some embodiments, R n The structure shown in (Formula 11) is preferably

[0019] In some embodiments, R n The structure shown in (Formula 12) is preferably

[0020] In some embodiments, R n The structure shown in (Formula 13) is preferably

[0021] In some embodiments, the number average molecular weight of the guanidine polymer may be 500 to 30,000.

[0022] In some embodiments, a may include two or more structural units represented by the general formula (A). Preferably, a includes two structural units represented by the general formula (A).

[0023] When a includes two structural units represented by the general formula (A), the molar ratio of the two structural units represented by the general formula (A) may be (1-100):1, preferably (1-3):1.

[0024] When a includes the structural unit represented by (Formula A1) and the structural unit represented by (Formula A2), the molar ratio of the structural unit represented by (Formula A1) to the structural unit represented by (Formula A2) may be (1-100):1, preferably (1-10):1, and more preferably 1:1.

[0025] When a includes the structural unit represented by (Formula A3) and the structural unit represented by (Formula A4), the molar ratio of the structural unit represented by (Formula A3) to the structural unit represented by (Formula A4) can be (1 to 10):1, preferably 2:1.

[0026] When a includes the structural unit represented by (Formula A4) and the structural unit represented by (Formula A5), the molar ratio of the structural unit represented by (Formula A4) to the structural unit represented by (Formula A5) can be (1 to 3):1, preferably 1:1.

[0027] When a includes the structural unit represented by (Formula A6) and the structural unit represented by (Formula A2), the molar ratio of the structural unit represented by (Formula A6) to the structural unit represented by (Formula A2) may be (1 to 100):1, preferably (1 to 10):1, and more preferably 1:1.

[0028] When a includes the structural unit represented by (Formula A6) and the structural unit represented by (Formula A4), the molar ratio of the structural unit represented by (Formula A6) to the structural unit represented by (Formula A4) can be 1:(1-5), preferably 1:3.

[0029]

[0030] When a includes two structural units represented by the general formula (A), Y in one structural unit represented by the general formula (A) n - Can be selected from Cl - In another structural unit represented by the general formula (A), Y n - Can be selected from H2PO4 - or CH3(CH2) 16 COO - .

[0031] In a preferred embodiment, any one of R and R' is hydrogen, and the other is the structural unit shown in (Formula 21), the structural unit shown in (Formula 22), the structural unit shown in (Formula 23), the structural unit shown in (Formula 24) or the structural unit shown in (Formula 25); preferably, any one of R and R' is hydrogen, and the other is the structural unit shown in (Formula 21), the structural unit shown in (Formula 22) or the structural unit shown in (Formula 24).

[0032] In some embodiments, R3 is preferably butyl, octyl or dodecyl.

[0033] In some embodiments, R4 is preferably ethylene.

[0034] In some embodiments, C2 to C 12 The alkyl group is preferably C11 alkyl.

[0035] In some embodiments, the substituted or unsubstituted C5-C8 cycloalkyl group in R5 is preferably a substituted or unsubstituted C5-C8 unsaturated cycloalkyl group, and more preferably a methyl-substituted C6 unsaturated cycloalkyl group, for example

[0036] In a preferred embodiment, the guanidine polymer has a structure shown in general formula (B),

[0037]

[0038] Among them, Y1 - and Y2 - Each independently is Cl - Br - 、HSO4 - 、HCO3 - 、H2PO4 - 、CH3COO - or CH3(CH2) 16 COO - , Y1 - and Y2 - The two are the same or different; m and n are natural numbers from 0 to 8, but m and n are not 0 at the same time; k is a natural number from 1 to 8;

[0039] R1 and R2 are each independently selected from one or more structural units having the structure shown in (Formula 11), the structure shown in (Formula 12), the structure shown in (Formula 13), the structure shown in (Formula 14), the structure shown in (Formula 15), the structure shown in (Formula 16) and the structure shown in (Formula 17), and R1 and R2 are the same structure or different structures;

[0040] R and R' are each independently selected from hydrogen, a structural unit represented by (Formula 21), a structural unit represented by (Formula 22), a structural unit represented by (Formula 23), a structural unit represented by (Formula 24) or a structural unit represented by (Formula 25), and R and R' are not hydrogen at the same time.

[0041] The present invention also provides a method for preparing the guanidine polymer as described above, comprising the following preparation steps:

[0042] (1) selecting at least one guanidine salt having a structure represented by the general formula (3) and at least one double-terminated diamine having a structure represented by the general formula (4) to carry out a condensation polymerization reaction;

[0043]

[0044] (2) The material obtained in step (1) is subjected to a capping reaction with a capping agent to obtain the guanidine salt polymer.

[0045] In step (1), the temperature of the condensation polymerization reaction can be 80 to 180°C.

[0046] In step (1), the condensation polymerization reaction time may be 0.5 to 10 h, preferably 2 to 6 h, for example, 3.5 h, 4.5 h, 5 h or 5.5 h.

[0047] In step (1), the molar ratio of the double-terminal amino diamine of the structure represented by the general formula (4) to the guanidine salt of the structure represented by the general formula (3) can be (0.5-2):1, preferably (0.8-1.2):1, and more preferably (0.95-1.05):1.

[0048] In step (1), the condensation polymerization reaction may be followed by a further cooling operation, preferably to below 160°C.

[0049] In step (1), the method for preparing the guanidine salt of the structure represented by the general formula (3) may include the following steps: reacting dicyandiamide or a guanidine compound with a Y-containing n - Acid or containing Y n - The salt reaction is done.

[0050] Wherein, the Y n - The salt may include Y n - of ammonium salt.

[0051] In step (1) of a preferred embodiment, when there are at least two types of the guanidine salt of the structure shown in the general formula (3) or the double-terminal amine diamine of the structure shown in the general formula (4), the guanidine salt of the structure shown in the general formula (3) and the double-terminal amine diamine of the structure shown in the general formula (4) are arbitrarily combined and subjected to a first condensation polymerization reaction respectively, and then the materials obtained after the first condensation polymerization reaction are mixed and subjected to a second condensation polymerization reaction. When this process is adopted, guanidine salts with large differences can be made into guanidine polymers connected by fragment structures, the structure of the product can be effectively controlled, and the synthesized guanidine polymer has multiple functions and better performance.

[0052] The temperature of the first condensation polymerization reaction may be 80-110°C, preferably 85-105°C, for example, 90°C, 95°C or 100°C.

[0053] The first condensation polymerization reaction time may be 0.5 to 3.5 hours, preferably 1 to 2.5 hours, for example, 1.5 hours.

[0054] The temperature of the second condensation polymerization reaction may be 140-180°C, preferably 165-180°C, for example, 170°C or 175°C.

[0055] The second condensation polymerization reaction time may be 0.5 to 6.5 h, preferably 2 to 5 h, for example, 3 h, 3.5 h or 4 h.

[0056] In step (2), the molar amount of the capping agent can be 1 / 10 to 1 / 2 of the total molar amount of the guanidine salt of the structure represented by the general formula (3), preferably 1 / 10 to 1 / 4, for example, 1 / 9, 1 / 6, 1 / 5 or 1 / 4.5.

[0057] In step (2), the end-capping reaction time may be 0.2 to 3 hours, preferably 0.4 to 2 hours, for example, 1.4 hours or 1.5 hours.

[0058] In step (2), the end-capping agent may include any one or more of monoepoxy-containing compounds, acid anhydride compounds, aldehyde compounds and isocyanate compounds, preferably monoepoxy-containing compounds, acid anhydride compounds or aldehyde compounds.

[0059] Wherein, the monoepoxy compound may include C4~C 12 The alkyl glycidyl ether preferably includes one or more of butyl glycidyl ether, octyl glycidyl ether and dodecyl glycidyl ether.

[0060] The acid anhydride compound may include phthalic anhydride and / or C4-C8 alkyl anhydride. Preferably, the C4-C8 alkyl anhydride includes succinic anhydride.

[0061] Wherein, the aldehyde compound may include R5CHO, wherein R5 is C2~C 12 alkyl, substituted or unsubstituted C5-C8 cycloalkyl, benzyl or phenethyl. 12 Alkyl is C 11 Preferably, the substituted or unsubstituted C5-C8 cycloalkyl is a substituted or unsubstituted C5-C8 unsaturated cycloalkyl, more preferably a methyl-substituted C6 unsaturated cycloalkyl, for example

[0062] Wherein, the isocyanate compound may include p-toluenesulfonyl isocyanate.

[0063] In step (2), the end-capping agent can be added dropwise or in batches.

[0064] In a preferred embodiment, the preparation method of the guanidine salt polymer comprises the following steps: selecting a guanidine salt of a structure shown in (Formula 31) and a guanidine salt of a structure shown in (Formula 32) and respectively carrying out a first condensation polymerization reaction with a double-terminal amine diamine of a structure shown in (Formula 41) and a double-terminal amine diamine of a structure shown in (Formula 42), wherein the temperature of the first condensation polymerization reaction does not exceed 80 to 180° C., the time of the first condensation polymerization reaction is 0.5 to 10 hours, and the ratio of the total molar amount of the double-terminal amine diamine to the total molar amount of the guanidine salt is (0.5 to 2): 1;

[0065]

[0066] The materials after the first condensation polymerization reaction are mixed, and a second condensation polymerization reaction is carried out for 0.5 to 4.5 hours, then the temperature is lowered to no more than 160° C., and the end-capping agent is added, wherein the molar amount of the end-capping agent is 1 / 10 to 1 / 2 of the total molar amount of the guanidine salt, and the end-capping reaction is carried out for 0.2 to 3 hours to obtain the guanidine salt polymer.

[0067] Among them, when Y1 - and Y2 - The same, R1 and R2 are the same, and the preparation process is carried out in the same reactor.

[0068] Among them, when Y1 - and Y2 - If at least one of the structures between R1 and R2 is different, the first condensation polymerization reaction is carried out in two reactors, and the second condensation polymerization reaction is carried out in one reactor.

[0069] The temperature of the first condensation polymerization reaction may be 80-110°C, preferably 85-105°C, for example, 90°C, 95°C or 100°C.

[0070] The first condensation polymerization reaction time may be 0.5 to 3.5 hours, preferably 1 to 2.5 hours, for example, 1.5 hours.

[0071] The temperature of the second condensation polymerization reaction may be 140-180°C, preferably 165-180°C, for example, 170°C or 175°C.

[0072] The second condensation polymerization reaction time may be 0.5 to 6.5 h, preferably 2 to 5 h, for example, 3 h, 3.5 h or 4 h.

[0073] In step (2), when the end-capping agent is butyl glycidyl ether, a reaction formula of the end-capping reaction is as follows:

[0074]

[0075] In step (2), when the end-capping agent is phthalic anhydride, a reaction formula of the end-capping reaction is as follows:

[0076]

[0077] In step (2), when the end-capping agent is benzaldehyde, a reaction formula of the end-capping reaction is as follows:

[0078]

[0079] According to the technical solution of the present invention, in step (1), the Y1 structure and Y2 structure of the guanidine salt can be selected according to different needs. For example, considering increasing the flame retardancy of the guanidine salt polymer, a guanidine salt with a phosphate structure can be selected; considering reducing the corrosiveness to iron materials, the chloride ion content can be reduced or a guanidine salt without chloride ions can be selected; considering reducing the viscosity of the guanidine salt polymer, a guanidine salt with a stearic acid structure can be selected; considering the better degradability of the guanidine salt polymer, a guanidine salt with a HCO3 structure can be selected - or CH3COO - Guanidine salt of structure; When the guanidine salt of structure shown in (Formula 31) and the guanidine salt of structure shown in (Formula 32) are used in combination, it is more conducive to adjusting the comprehensive performance of the guanidine salt polymer. When the preparation raw materials include guanidine stearate, the guanidine stearate polymer intermediate obtained after the first condensation polymerization reaction has poor compatibility with the guanidine salt polymer intermediate obtained with other guanidine salts as raw materials. Therefore, guanidine stearate polymer intermediates are generally not used as raw materials to prepare guanidine polymers in this field. The present application creatively polymerizes the guanidine stearate polymer intermediate with poor compatibility with other guanidine salt polymer intermediates, which not only effectively solves this problem, but also promotes the obtained guanidine polymer to have multiple functions, and its antibacterial, corrosion resistance and surface smoothness and other properties are all excellent.

[0080] The present invention also provides a graft polymer, wherein the polymerization monomer of the graft polymer comprises the guanidine polymer as described above and / or the guanidine polymer prepared by the preparation method of the guanidine polymer as described above.

[0081] In some embodiments, the polymerized monomer of the grafted polymer may further include any one or more of a polymer grafted with maleic anhydride, a polymer with maleic anhydride as a polymerized monomer, a polymer grafted with a monoepoxy-containing compound, and a polymer with a monoepoxy-containing compound as a polymerized monomer.

[0082] The polymer grafted with maleic anhydride may include polyolefin grafted with maleic anhydride, preferably polyethylene grafted with maleic anhydride and / or polypropylene grafted with maleic anhydride.

[0083] The polymer with maleic anhydride as a polymerization monomer may include olefin-maleic anhydride copolymer, preferably styrene-maleic anhydride copolymer.

[0084] The polymer grafted with the monoepoxy-containing compound may include polyolefin grafted with glycidyl methacrylate, preferably polyethylene grafted with glycidyl methacrylate and / or polypropylene grafted with glycidyl methacrylate.

[0085] The polymer containing a monoepoxy-containing compound as a polymerization monomer may include an olefin-acrylate-glycidyl methacrylate copolymer, preferably a styrene-acrylate-glycidyl methacrylate copolymer.

[0086] In some embodiments, the grafted polymer has a structure similar to the following:

[0087]

[0088] In contrast, if a non-terminated guanidine polymer is used in the reaction, a cross-linked structure similar to the following fragment will be obtained. This cross-linked structure will cause the processing performance of the grafted polymer to drop sharply, or even make it impossible to process.

[0089]

[0090] The present invention also provides a method for preparing the graft polymer as described above, which specifically comprises the following steps: mixing the polymerization monomers of the graft polymer for reaction.

[0091] In some embodiments, the temperature of the mixing reaction may be conventional in the art, generally higher than the melting temperature of the polymerization monomer of the graft polymer, preferably 150-300°C.

[0092] When the polymerizable monomer of the graft polymer includes a polyethylene graft polymer, the temperature of the mixing reaction may be 150-200° C., preferably 170-180° C. The polyethylene graft polymer may include polyethylene graft maleic anhydride and / or polyethylene graft glycidyl methacrylate.

[0093] When the polymerizable monomer of the graft polymer includes a polypropylene graft polymer, the temperature of the mixing reaction may be 170-200° C., preferably 170-180° C. The polypropylene graft polymer may include polypropylene grafted maleic anhydride and / or polypropylene grafted glycidyl methacrylate.

[0094] When the polymerizable monomers of the graft polymer include polymers with styrene and / or acrylate as polymerizable monomers, the temperature of the mixing reaction is 150-200° C., preferably 170-180° C. Wherein, the polymers with styrene and / or acrylate as polymerizable monomers include styrene-maleic anhydride copolymer and / or styrene-acrylate-glycidyl methacrylate copolymer.

[0095] In some embodiments, the mixing reaction time may be 3 to 30 minutes, preferably 5 to 10 minutes, and more preferably 6 minutes.

[0096] In some embodiments, when the polymerization monomer of the grafted polymer includes the polymer grafted with maleic anhydride or the polymer with maleic anhydride as the polymerization monomer, the mass ratio of the guanidine polymer to "the polymer grafted with maleic anhydride or the polymer with maleic anhydride as the polymerization monomer" may be 1:(4~200), for example, 1:7, 1:10, 1:40 or 1:100.

[0097] In some embodiments, when the polymerization monomers of the grafted polymer include the polymer grafted with a monoepoxy-containing compound and the polymer with a monoepoxy-containing compound as a polymerization monomer, the mass ratio of the guanidine polymer to "the polymer grafted with a monoepoxy-containing compound and the polymer with a monoepoxy-containing compound as a polymerization monomer" may be 1:(4~200), for example, 1:20.

[0098] The present invention also provides a use of the guanidine polymer and / or the graft polymer as described above as a raw material in the preparation of an antibacterial product.

[0099] On the basis of being in accordance with the common sense in the art, the above-mentioned preferred conditions can be arbitrarily combined to obtain the preferred embodiments of the present invention.

[0100] The reagents and raw materials used in the present invention are commercially available.

[0101] The positive and progressive effects of the present invention are:

[0102] (1) During the research and development process, it was found that the selection of monoepoxy-containing compounds, anhydride compounds, aldehyde compounds and isocyanate compounds as end-capping agents can improve the end-capping rate and allow the end-capping reaction to be carried out under relatively low temperature and relatively mild conditions. Lower temperature conditions are conducive to expanding the selection range of end-capping agents. For example, the length of the relatively inert end of the fatty chain can be shortened, and the selection of end-capping agents with shorter fatty chain lengths is conducive to increasing the compatibility of the end-capping agent with the guanidine polymer, thereby further improving the efficiency of the end-capping reaction and increasing the end-capping rate. The expansion of the end-capping agent selection range is conducive to selecting low-corrosive, low-irritating, low-toxic, and relatively safer end-capping agents. For example, butyl glycidyl ether is a commonly used active diluent for epoxy resins, which is low in toxicity and harm. The selection of butyl glycidyl ether as an end-capping agent is conducive to improving the safety of the production process. The increase in the end-capping rate means that the content of residual end-capping agents in the guanidine polymer product after end-capping is reduced, which will significantly improve the quality of the end-capped guanidine polymer product.

[0103] The invention avoids the problems of low end-capping efficiency, high monomer residue, high corrosiveness, high irritation and high toxicity of amine substances in the preparation process and residual amine substances in the use of the end-capped guanidine salt polymer brought about by the technology of non-polar long-chain aliphatic monoamine structure end-capping guanidine salt oligomer in patent CN106800652B.

[0104] (2) By adjusting and controlling the amount and method of adding the capping agent, the guanidine salt polymer is capped on one side rather than both sides, thereby ensuring that the capped guanidine salt polymer is able to participate in subsequent reactions, such as grafting reactions, and avoiding the formation of a cross-linked structure.

[0105] (3) Through Y n - , R n The selection of groups makes the obtained guanidine polymer have more flexible comprehensive properties, which provides a larger selection space for the guanidine polymer after single-side end-capping to participate in subsequent grafting reactions, greatly improving the application value of this case.

[0106] Therefore, the new guanidine salt polymer preparation technology provided by the present invention overcomes the problems of low end-capping efficiency caused by using long-chain aliphatic amine substances for end-capping, as well as the high corrosiveness, high irritation, high toxicity and the like of the long-chain aliphatic amine substances themselves, thereby improving the safety of the preparation process; the prepared guanidine salt polymer has less residual end-capping monomers, thus having better product safety and improving product quality; the prepared guanidine salt polymer avoids the disadvantage of the prior art that the multi-functional guanidine salt polymer is very easy to generate cross-links during the bonding reaction with the polymer due to the reduced reaction functionality, thereby improving the product quality of the grafted polymer produced subsequently. DETAILED DESCRIPTION

[0107] The present invention is further described below by way of examples, but the present invention is not limited to the scope of the examples. The experimental methods in the following examples without specifying specific conditions are carried out according to conventional methods and conditions, or selected according to the product specifications.

[0108] Hereinafter, exemplary embodiments of the present disclosure will be described.

[0109] Unless otherwise specified, the experimental methods used in the following examples are conventional methods.

[0110] Example 1

[0111] Take 38.2g of guanidine hydrochloride (0.4mol) and 62.8g of guanidine phosphate (0.4mol) and add them to two three-necked flasks respectively. Then add 54.5g of m-phenylenediamine (0.4mol) to the flask containing guanidine hydrochloride, and add 46.5g of 1,6-hexanediamine (0.4mol) to the flask containing guanidine phosphate. Under nitrogen protection, stir and heat to 90°C for 2.5 hours. Then combine the materials in the two flasks into one flask, gradually heat to 170°C and continue to react for 2 hours. The intermediate product of the reaction at this time is marked as guanidine polymer-Y. Finally, lower the temperature to 158°C, add 38.8g of dodecyl glycidyl ether (0.16mol) dropwise within 1.5 hours, and then react for another 0.5 hours, pour out while hot, and obtain guanidine polymer-1.

[0112] Example 2

[0113] Take 62.8g of guanidine phosphate (0.4mol) and 68.7g of guanidine stearate (0.2mol) and add them to two three-necked flasks respectively. Then add 54.5g of m-phenylenediamine (0.4mol) to the flask containing guanidine phosphate, and add 23.2g of 1,6-hexanediamine (0.2mol) to the flask containing guanidine stearate. Stir and heat to 105°C under nitrogen protection and react for 2 hours. Then combine the materials in the two flasks into one flask, gradually heat to 175°C and continue to react for 3 hours. Finally, lower the temperature to 155°C, add 14.8g of phthalic anhydride (0.1mol) in 4 times within 1 hour, and then react for 0.5 hours, pour out while hot, and obtain guanidine salt polymer-2.

[0114] Example 3

[0115] Take 48.4g guanidine carbonate (0.4mol) and 137.4g guanidine stearate (0.4mol) and add them to two three-necked flasks respectively. Then add 40.8g pentamethylenediamine (0.4mol) to the flask containing guanidine carbonate, and also add 40.8g pentamethylenediamine (0.4mol) to the flask containing guanidine stearate, stir and heat to 95°C under nitrogen protection, and react for 1.5 hours. Then combine the materials in the two flasks into one flask, gradually heat to 170°C and continue to react for 3 hours. Finally, lower the temperature to 150°C, add 26g butyl glycidyl ether (0.2mol) dropwise within 1.5 hours, and then react for another 0.5 hours, pour out while hot, and obtain guanidine salt polymer-3.

[0116] Example 4

[0117] 38.2g of guanidine hydrochloride (0.4mol) was added to a three-necked flask, and then 46.4g of 1,6-hexanediamine (0.4mol) was added. Under nitrogen protection, the mixture was stirred and heated to 90°C for 1.5 hours. The temperature was then gradually raised to 175°C and the reaction continued for 4 hours. Finally, the temperature was lowered to 158°C, 10.5g of butyl glycidyl ether (0.08mol) was added dropwise within 1.5 hours, and the mixture was reacted for another 0.5 hour. The mixture was poured out while hot to obtain guanidine salt polymer-4.

[0118] Example 5

[0119] 38.2 g of guanidine hydrochloride (0.4 mol) was added to a three-necked flask, and then 58.4 g of triethylenetetramine (0.4 mol) was added. Under nitrogen protection, the mixture was stirred and heated to 85°C for 1.5 hours. The mixture was then gradually heated to 165°C and the reaction was continued for 3 hours. Finally, the temperature was lowered to 150°C, 10 g (0.094 mol) of benzaldehyde was added dropwise within 1 hour, and the reaction was continued for another 25 minutes. The mixture was poured out while hot to obtain guanidine salt polymer-5.

[0120] Example 6

[0121] 38.2 g of guanidine hydrochloride (0.4 mol) was added to a three-necked flask, and then 62.2 g of 1,8-diamino-3,6-dioxaoctane (0.42 mol) was added. Under nitrogen protection, the mixture was stirred and heated to 90°C for 1.0 hour. The temperature was then gradually raised to 170°C and the reaction was continued for 4 hours. Finally, the temperature was lowered to 150°C, 12 g of butyl glycidyl ether (0.092 mol) was added dropwise within 1.5 hours, and then the reaction was continued for 35 minutes. The mixture was poured out while hot to obtain guanidine salt polymer-6.

[0122] Example 7

[0123] 62.8g of guanidine phosphate (0.4mol) was added to a three-necked flask, and then 48.0g of 1,3-cyclohexanediamine (0.42mol) was added. Under nitrogen protection, the mixture was stirred and heated to 100°C for 1.5 hours. The temperature was then gradually raised to 170°C and the reaction continued for 3 hours. Finally, the temperature was lowered to 155°C, and 16g of octyl glycidyl ether (0.086mol) was added dropwise for 1.5 hours to react. After another 35 minutes, the mixture was poured out while hot to obtain guanidine polymer-7.

[0124] Example 8

[0125] Take 38.2g of guanidine hydrochloride (0.4mol) and 62.8g of guanidine phosphate (0.4mol) and add them to two three-necked flasks respectively. Then add 54.5g of m-phenylenediamine (0.4mol) to the flask containing guanidine hydrochloride, and add 46.5g of 1,6-hexanediamine (0.4mol) to the flask containing guanidine phosphate. Under nitrogen protection, stir and heat to 90°C and react for 2.5 hours. Then combine the materials in the two flasks into one flask, gradually heat to 170°C and continue to react for 2 hours. Finally, lower the temperature to 158°C, add 31.5g of p-toluenesulfonyl isocyanate (0.16mol) dropwise within 1.5 hours, and then react for another 0.5 hours, pour out while hot, and obtain guanidine salt polymer-8.

[0126] Example 9

[0127] Take 19.1g of guanidine hydrochloride (0.2mol) and 31.4g of guanidine phosphate (0.2mol), add them to two three-necked flasks respectively, then add 23.2g of 1,6-hexanediamine (0.2mol) to each flask, stir and heat to 90℃ under nitrogen protection, and react for 1.5 hours. Then combine the materials in the two flasks into one flask, gradually heat to 175℃ and continue to react for 4 hours. Finally, lower the temperature to 158℃, add 10.5g of butyl glycidyl ether (0.08mol) dropwise within 1.5 hours, then react for another 0.5 hours, pour out while hot, and obtain guanidine salt polymer-9.

[0128] Example 10

[0129] Take 9.55g of guanidine hydrochloride (0.1mol) and 103.1g of guanidine stearate (0.3mol) and add them to two three-necked flasks respectively, then add 11.6g of 1,6-hexanediamine (0.1mol) to the flask containing guanidine hydrochloride, and add 34.8g of 1,6-hexanediamine (0.3mol) to the flask containing guanidine stearate, stir and heat to 90°C under nitrogen protection, and react for 1.5 hours. Then combine the materials in the two flasks into one flask, gradually heat to 175°C and continue to react for 4 hours. Finally, lower the temperature to 158°C, add 10.5g of butyl glycidyl ether (0.08mol) dropwise within 1.5 hours, and then react for another 0.5 hours, pour out while hot, and obtain guanidine polymer-10.

[0130] Embodiment 11

[0131] 38.2 g of guanidine hydrochloride (0.4 mol) was added to a three-necked flask, and then 58.4 g of triethylenetetramine (0.4 mol) was added. Under nitrogen protection, the mixture was stirred and heated to 85°C for 1.5 hours. The mixture was then gradually heated to 165°C and the reaction was continued for 3 hours. Finally, the temperature was lowered to 150°C, and 13 g (0.094 mol) of 2,4-dimethyl-3-cyclohexenecarboxaldehyde was added dropwise within 1 hour, and then the reaction was continued for another 25 minutes. The mixture was poured out while hot to obtain guanidine salt polymer-11.

[0132] Example 12

[0133] 38.2 g of guanidine hydrochloride (0.4 mol) was added to a three-necked flask, and then 46.4 g of 1,6-hexanediamine (0.4 mol) was added. Under nitrogen protection, the mixture was stirred and heated to 90°C for 1.5 hours. The temperature was then gradually raised to 175°C and the reaction continued for 4 hours. Finally, the temperature was lowered to 158°C, 14.8 g of lauryl aldehyde (0.08 mol) was added dropwise within 1.5 hours, and the reaction was continued for another 0.5 hours. The mixture was poured out while hot to obtain guanidine salt polymer-12.

[0134] Embodiment 13

[0135] 103.1 g of guanidine stearate (0.3 mol) was added to a three-necked flask, and then 34.8 g of hexamethylenediamine (0.3 mol) was added. Under nitrogen protection, the mixture was stirred and heated to 90°C for 1.5 hours. The mixture was then gradually heated to 175°C and the reaction was continued for 4 hours. Finally, the temperature was lowered to 158°C, 10.5 g of butyl glycidyl ether (0.08 mol) was added dropwise within 1.5 hours, and the reaction was continued for another 0.5 hour. The mixture was poured out while hot to obtain guanidine polymer-13.

[0136] Comparative Example 1 (Compared with Example 2)

[0137] Take 62.8g guanidine phosphate (0.4mol) and 68.7g guanidine stearate (0.2mol) and add them to two three-necked flasks respectively. Then add 54.5g m-phenylenediamine (0.4mol) to the flask containing guanidine phosphate, and add 23.2g 1,6-hexanediamine (0.2mol) to the flask containing guanidine stearate. Stir and heat to 105℃ under nitrogen protection and react for 2 hours. Then combine the materials in the two flasks into one flask, gradually heat to 175℃ and continue to react for 3 hours. Finally, add 18.5g (0.1mol) dodecylamine and react for 2.0 hours, pour out while hot to obtain guanidine salt polymer-pair 1.

[0138] Comparative Example 2 (Compared with Example 4)

[0139] 38.2 g of guanidine hydrochloride (0.4 mol) was added to a three-necked flask, and then 46.4 g of 1,6-hexanediamine (0.4 mol) was added. Under nitrogen protection, the mixture was stirred and heated to 90°C for 1.5 hours. The temperature was then gradually raised to 175°C and the reaction was continued for 4 hours. Finally, 14.9 g of dodecylamine (0.08 mol) was added and the reaction was continued for 2.0 hours. The mixture was poured out while hot to obtain guanidine salt polymer-pair 2.

[0140] Comparative Example 3

[0141] 38.2 g of guanidine hydrochloride (0.4 mol) was added to a three-necked flask, and then 46.4 g of 1,6-hexanediamine (0.4 mol) was added. Under nitrogen protection, the mixture was stirred and heated to 90°C for 1.5 hours. The mixture was then gradually heated to 175°C and continued to react for 4 hours. The mixture was poured out while hot to obtain guanidine salt polymer-pair 3.

[0142] Comparative Example 4

[0143] 38.2 g of guanidine hydrochloride (0.4 mol) was added to a three-necked flask, and then 46.4 g of 1,6-hexanediamine (0.4 mol) was added. Under nitrogen protection, the mixture was stirred and heated to 90°C for 1.5 hours. The temperature was then gradually raised to 175°C and the reaction was continued for 4 hours. Finally, 17.4 g of pyromellitic anhydride (0.08 mol) was added and the reaction was continued for 2.0 hours. The mixture was poured out while hot to obtain guanidine salt polymer-p-4.

[0144] Application Example 1

[0145] Take 10g of guanidine salt polymer-1 and 40g of polypropylene grafted maleic anhydride (maleic anhydride grafting rate 2.0%), mix them, add them into a Haake internal mixer, and melt react at 180°C for 6 minutes to obtain polypropylene grafted guanidine salt polymer-1.

[0146] Application Example 2

[0147] 6 g of guanidine salt polymer-4 and 44 g of polyethylene grafted maleic anhydride (maleic anhydride grafting rate 1%) were mixed and added into a Haake internal mixer and melt-reacted at 170° C. for 6 min to obtain polyethylene grafted guanidine salt polymer-1.

[0148] Application Example 3

[0149] 10 g of guanidine salt polymer-4 and 40 g of styrene-maleic anhydride copolymer (maleic anhydride content 5%) were mixed and added into a Haake internal mixer for melting reaction at 170° C. for 6 min to obtain styrene-maleic anhydride copolymer grafted guanidine salt polymer-1.

[0150] Application Example 4

[0151] Take 10g of guanidine polymer-4 and 40g of styrene-acrylate-glycidyl methacrylate copolymer (glycidyl methacrylate content 5%), mix them, add them into a Haake internal mixer, and melt react at 180°C for 6min to obtain styrene-acrylate-glycidyl methacrylate copolymer grafted with guanidine polymer-1.

[0152] Application Example 5

[0153] Take 10g of guanidine salt polymer-4 and 40g of polypropylene grafted maleic anhydride (maleic anhydride grafting rate 2.0%), mix them, add them into a Haake internal mixer, and melt react at 180°C for 6 minutes to obtain polypropylene grafted guanidine salt polymer-2.

[0154] Application Example 6

[0155] Take 10g of guanidine salt polymer-10 and 40g of polypropylene grafted maleic anhydride (maleic anhydride grafting rate 2.0%), mix them, add them into a Haake internal mixer, and melt react at 180°C for 6 minutes to obtain polypropylene grafted guanidine salt polymer-3.

[0156] Application Example 7

[0157] Take 10g of guanidine salt polymer-13 and 40g of polypropylene grafted maleic anhydride (maleic anhydride grafting rate 2.0%), mix them, add them into a Haake internal mixer, and melt react at 180°C for 6 minutes to obtain polypropylene grafted guanidine salt polymer-4.

[0158] In the above application examples, the obtained guanidine salt grafted polymer has good processing fluidity, is completely soluble in the solvent, and has no cross-linked product. The grafting efficiency of the guanidine salt polymer is above 93%.

[0159] Application Example 1

[0160] 10 g of uncapped guanidine salt polymer-Y (intermediate product in Example 1) and 40 g of polypropylene grafted maleic anhydride (maleic anhydride grafting rate 2.0%) were mixed and added into a Haake internal mixer and melt-reacted at 180° C. for 6 min to obtain polypropylene grafted guanidine salt polymer-5.

[0161] Application Example 2

[0162] 6 g of uncapped guanidine salt polymer-Y (intermediate product in Example 1) and 44 g of polyethylene grafted maleic anhydride (maleic anhydride grafting rate 1%) were mixed and added to a Haake internal mixer and melt-reacted at 170° C. for 6 min to obtain polyethylene grafted guanidine salt polymer-2.

[0163] Application Example 3

[0164] 10 g of uncapped guanidine polymer-Y (intermediate product in Example 1) and 40 g of styrene-maleic anhydride copolymer (maleic anhydride content 5%) were mixed and added to a Haake internal mixer for melt reaction at 170° C. for 6 min to obtain styrene-maleic anhydride copolymer grafted guanidine polymer-2.

[0165] Application Example 4

[0166] Take 10g of uncapped guanidine polymer-Y (intermediate product in Example 1) and 40g of styrene-acrylate-glycidyl methacrylate copolymer (glycidyl methacrylate content 5%), mix them, add them into a Haake internal mixer, and melt react at 180°C for 6min to obtain styrene-acrylate-glycidyl methacrylate copolymer grafted guanidine polymer-2.

[0167] The above application control examples 1 to 4 all have serious cross-linking phenomenon, and the reaction products are basically unable to melt and flow, and their state is cross-linked powder. By comparison, it can be seen that the new end-capping technology disclosed by the present invention greatly improves the end-capping rate of guanidine salt polymers, avoiding the problems of processing difficulties and even cross-linking of guanidine salt polymers in subsequent use.

[0168] Effect Example 1

[0169] The end-capping rate of the guanidine polymer obtained in the above examples and comparative examples was tested, and the results are shown in Table 1. *: The end-capping rate is the ratio of the number of end-capped guanidine polymers to the total number of guanidine polymers. The structure of the guanidine polymer was characterized by mass spectrometry, and the end group structure and the number of corresponding structures were tested.

[0170] Table 1

[0171] serial number Polymer Type End-capping rate* Example 1 Guanidine polymer-1 95％ Example 2 Guanidine polymer-2 91％ Example 3 Guanidine polymer-3 95％ Example 4 Guanidine polymer-4 97％ Example 5 Guanidine polymer-5 85％ Example 6 Guanidine polymer-6 95％ Example 7 Guanidine polymer-7 92％ Example 8 Guanidine polymer-8 80％ Example 9 Guanidine polymer-9 97％ Example 10 Guanidine polymer-10 97％ Embodiment 11 Guanidine polymer-11 90％ Example 12 Guanidine polymer-12 93％ Comparative Example 1 Guanidine polymer-to-1 40％ Comparative Example 2 Guanidine polymer-to-2 30％ Comparative Example 3 Guanidine polymer-to-3 - Comparative Example 4 Guanidine polymer-to-4 -

[0172] The “-” in Table 1 means that when the graft polymer is prepared using the guanidine salt polymer as a raw material, cross-linking occurs, and therefore this group of data is not tested.

[0173] Effect Example 2

[0174] The minimum inhibitory concentration and dissolution rate of the guanidine salt polymers obtained in the above examples and comparative examples were tested. The results are shown in Table 2.

[0175] Among them, the test method for the minimum inhibitory concentration is the Miller-Hayden broth microdilution method recommended by CLSI.

[0176] The dissolution rate test method is as follows: (1) 10 g of the guanidine salt polymer obtained in each of the above embodiments and comparative examples are selected and mixed with 40 g of polypropylene grafted maleic anhydride (maleic anhydride grafting rate of 2.0%). Add the mixture into a Haake internal mixer and melt react at 180° C. for 6 minutes to obtain the corresponding polypropylene grafted guanidine salt polymer. (2) Dissolution rate test process: Grind the polypropylene grafted guanidine salt polymer to obtain a powdered polypropylene grafted guanidine salt polymer. Weigh 0.5 g of powdered material, put it into 250 mL of deionized water, and stir it magnetically at 35-40° C. for 1 hour. After that, let it stand at 23-27° C. for 24 hours, and then filter it with filter paper at low pressure. The filtrate contains unreacted guanidine polymer. The filtration residue on the filter paper is vacuum dried at 40° C. and then weighed. The weight of the raw material minus the weight of the dried residue is recorded as the lost weight. The lost weight is divided by the weight of the added guanidine polymer, and the ratio obtained is recorded as the dissolution rate.

[0177] Table 2

[0178]

[0179] The “-” in Table 2 means that when the graft polymer is prepared using the guanidine salt polymer as the raw material, cross-linking occurs, and therefore this group of data is not tested.

[0180] Effect Example 3

[0181] The corrosiveness of the guanidine salt polymers obtained in Examples 3, 4 and 10 above was tested. The results are shown in Table 3.

[0182] The test method is: 304 stainless steel test piece (50×10×3mm 3 ) After polishing, cleaning and drying, the above-synthesized guanidine polymer-3, guanidine polymer-4 or guanidine polymer-10 are respectively covered thereon, placed in a 200°C oven, treated for 24 hours, and then the guanidine polymer on the steel sheet is removed, cleaned with water and dried. The mass of the sample before and after treatment and the appearance of the stainless steel are weighed using an analytical balance to evaluate the corrosiveness of the guanidine polymer to the steel.

[0183] Table 3

[0184] <![CDATA[Weight loss rate (g / m 2 )]]> Appearance after treatment Guanidine polymer-3 0.02 No signs of corrosion Guanidine polymer-4 2.56 Corrosion, more spots Guanidine polymer-10 0.48 Slight corrosion, few spots

[0185] The results show that the combination of guanidine stearate and guanidine hydrochloride can improve the strong corrosion of guanidine salt polymer prepared solely from guanidine hydrochloride to steel, and has no significant effect on the antibacterial effect.

[0186] Effect Example 4

[0187] (1) The grafted guanidine salt polymers prepared in Examples 5 to 7 were mixed with PP and processed to prepare injection molded plates (150×100×3.2 mm 3 ); Injection molding plate preparation conditions: barrel temperature is 230 ℃, nozzle temperature is 190 ℃, mold temperature is 60 ℃; the content of guanidine polymer in the injection molding plate is 1.5% (by weight);

[0188] (2) The test objects are injection molded plates made of pure PP and three injection molded plates made in step (1);

[0189] (3) The cross-hatch test method under a load of 10N was used to measure the color change (L value) caused by the scratch stress whitening, that is, ΔL was used to evaluate the scratch resistance of the material. The results are shown in Table 4. (The material surface yields under the action of indentation and sliding force or lateral (lateral) force, resulting in ductile / brittle failure and causing scratches. In scratches, uneven surfaces will produce uneven light scattering and "scratch whitening" phenomenon.)

[0190] Table 4

[0191]

[0192]

[0193] The results show that when the raw materials for preparing the guanidine salt polymer include guanidine stearate, the plastic prepared using this type of guanidine salt polymer as a raw material has better surface finish.

[0194] The above application control examples all have serious cross-linking phenomenon, and the reaction products are basically unable to melt and flow, and their state is cross-linked powder. By comparison, it can be seen that the new end-capping technology disclosed by the present invention greatly improves the end-capping rate of guanidine salt polymers, and avoids the processing difficulties and even cross-linking problems caused by multi-functional reactions in the subsequent use of guanidine salt polymers.

[0195] Finally, it should be noted that in the present invention, the terms "comprises", "includes" or any other variations thereof are intended to cover non-exclusive inclusion, so that a process, method, article or apparatus that includes a series of elements includes not only those elements, but also includes other elements that are not explicitly listed, or also includes elements that are inherent to such process, method, article or apparatus.

[0196] Although the present disclosure has been disclosed above through the description of the specific embodiments of the present disclosure, it should be understood that those skilled in the art can design various modifications, improvements or equivalents to the present disclosure within the spirit and scope of the attached scheme. These modifications, improvements or equivalents should also be considered to be included in the scope of protection claimed by the present disclosure.

Claims

1. A guanidine polymer, characterized in that The guanidine polymer has a structure shown in general formula (B), Among them, Y1 - and Y2 - Each independently is Cl - Br - 、HSO4 - 、HCO3 - 、H2PO4 - 、CH3COO - or CH3(CH2) 16 COO - , Y1 - and Y2 - The two are the same or different; m and n are natural numbers from 0 to 8, but m and n are not 0 at the same time; k is a natural number from 1 to 8; R1 and R2 are each independently selected from one or more structural units having the structure shown in (Formula 11), the structure shown in (Formula 13), the structure shown in (Formula 14), the structure shown in (Formula 15), the structure shown in (Formula 16) and the structure shown in (Formula 17), and R1 and R2 are the same structure or different structures; Wherein, R and R' are each independently selected from hydrogen, the structural unit represented by (Formula 21), the structural unit represented by (Formula 22), the structural unit represented by (Formula 23) or the structural unit represented by (Formula 24), and R and R' are not hydrogen at the same time; R3 is butyl, octyl or dodecyl; R4 is C2 alkylene; R5 is C 11 Alkyl, phenyl, benzyl Base or 2. The guanidine polymer according to claim 1, characterized in that The guanidine polymer meets the following conditions: Y1 - Cl - ;Y2 - H2PO4 - ; R1 has the structure shown in (Formula 16) R2 is a structural unit having a structure shown in (Formula 13) Structural unit 3. The guanidine polymer according to claim 1, characterized in that The guanidine polymer meets the following conditions: Y1 - Cl - ;Y2 - CH3(CH2) 16 COO - ; R1 has the structure shown in (Formula 16) R2 is a structural unit having a structure shown in (Formula 13) Structural unit 4. The guanidine polymer according to claim 1, characterized in that The guanidine polymer meets the following conditions: Y1 - HCO3 - ;Y2 - CH3(CH2) 16 COO - ; The structure shown in (Formula 13) in R1 and R2 is 5. The guanidine polymer according to claim 1, characterized in that The guanidine polymer meets the following conditions: Y1 - and Y2 - Cl - ; The structure shown in (Formula 13) in R1 and R2 is 6. The guanidine polymer according to claim 1, characterized in that The guanidine polymer meets the following conditions: Y1 - and Y2 - Cl - ; The structure shown in (Formula 11) in R1 and R2 is 7. The guanidine polymer according to claim 1, characterized in that The guanidine polymer meets the following conditions: Y1 - and Y2 - H2PO4 - ; R1 and R2 have the structure shown in (Formula 14) structural unit.

8. A method for preparing a guanidine polymer according to any one of claims 1 to 7, characterized in that: The preparation method comprises the following steps: (1) Add the defined Y1 into the reactor - and Y2 - Guanidine salt of structure; (2) Selecting double-terminal amine diamines with structures of NH2-R1-NH2 and NH2-R2-NH2, and mixing them with Y1-containing diamines at a molar ratio of diamine to guanidine salt of 0.5 to 2.0 respectively. - and Y2 - The guanidine salt of the structure is subjected to condensation polymerization, the reaction temperature is 80°C to 180°C, and the reaction time is 0.5 to 10 hours; (3) combining the materials after the reaction in step (2), continuing the reaction for 0.5 to 4.5 hours, then cooling to no more than 160° C., adding a capping agent in an amount of 1 / 10 to 1 / 2 of the total molar number of the guanidine salt, and continuing the reaction for 0.2 to 3 hours to obtain the guanidine salt polymer; The end-capping agent in step (3) is a compound having one end that can react with an amine group and the other end that is relatively inert; the end-capping agent is butyl glycidyl ether, octyl glycidyl ether, dodecyl glycidyl ether, phthalic anhydride, succinic anhydride, benzaldehyde, phenylacetaldehyde, lauryl aldehyde, or privet aldehyde.

9. The method for preparing a guanidine polymer according to claim 8, characterized in that: Y1 - and Y2 - The structures are the same, R1 and R2 are also the same, and the preparation process is carried out in the same reactor.

10. The method for preparing a guanidine polymer according to claim 8, characterized in that: Y1 - and Y2 - If at least one of the structures between R1 and R2 is different, step (1) and step (2) are carried out in two reactors, and step (3) is carried out in one reactor.

11. The method for preparing a guanidine polymer according to claim 8, 9 or 10, characterized in that: Prior to step (1), HCl, HBr, H2SO4, H2CO3, acetic acid, H3PO4 or stearic acid, or their corresponding salts, are directly or indirectly reacted with dicyandiamide or guanidine compound to obtain a determined acid radical ion Y1 - and Y2 - The structure of the guanidine salt.

12. The method for preparing a guanidine polymer according to claim 8, 9 or 10, characterized in that: The end-capping agent in step (3) is introduced by slowly dropping or gradually adding in batches.

13. The use of the guanidine polymer according to any one of claims 1 to 7, characterized in that: The guanidine salt polymer is grafted with other polymers to obtain a grafted polymer containing the guanidine salt polymer with good processing performance.

14. The use of the guanidine polymer according to claim 13, characterized in that: The guanidine salt polymer is subjected to a grafting reaction with polyethylene grafted maleic anhydride or polyethylene grafted glycidyl methacrylate to obtain a polyethylene grafted guanidine salt polymer; Alternatively, the guanidine salt polymer is grafted with polypropylene grafted with maleic anhydride, or polypropylene grafted with glycidyl methacrylate to obtain a polypropylene grafted with guanidine salt polymer; Alternatively, the guanidine salt polymer reacts with a styrene-maleic anhydride copolymer to obtain a styrene-maleic anhydride copolymer grafted guanidine salt polymer; Alternatively, the guanidine salt polymer is grafted with styrene-acrylate-glycidyl methacrylate copolymer to obtain styrene-acrylate-glycidyl methacrylate copolymer grafted guanidine salt polymer.

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