CN112521600A - Guanidine salt polymer and preparation method and application thereof - Google Patents
Guanidine salt polymer and preparation method and application thereof Download PDFInfo
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- CN112521600A CN112521600A CN202011268091.9A CN202011268091A CN112521600A CN 112521600 A CN112521600 A CN 112521600A CN 202011268091 A CN202011268091 A CN 202011268091A CN 112521600 A CN112521600 A CN 112521600A
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Abstract
The invention discloses a guanidine salt polymer, a preparation method and application thereof, wherein the guanidine salt polymer has a characteristic structure shown in a formula 1:
when in preparation, Y is respectively added into a reaction kettle1And Y2Guanidinium salt of structure (II) followed by the selection of structure NH2‑R1‑NH2And NH2‑R2‑NH2With the amine-terminated diamine of (a) and Y1And Y2And respectively carrying out condensation polymerization on the guanidine salts with the structures, combining the materials, continuing to carry out condensation reaction, then cooling to a temperature not higher than 160 ℃, adding a capping agent with one end capable of reacting with an amino group and the other end relatively inert, and continuing to react for 0.2-3 hours to obtain the guanidine salt polymer shown in the formula 1. The guanidine salt polymer can be grafted with other polymers to obtain the productGraft polymer with cross-linking structure and good processing property.
Description
Technical Field
The invention relates to the technical field of high molecular compounds, in particular to a guanidinium polymer, a preparation method and application thereof, belonging to the international patent classification table C08G 73/00.
Background
Microorganisms are closely related to human life. Although most bacteria are beneficial to humans, a small number of species of germs and viruses can have a significant negative impact on human daily life and even life. Therefore, the vigorous development of antibacterial and antiviral harmful microorganism-resistant materials is of great significance to the public health and health industry of human beings.
It is known in the art that guanidinium polymers have an extremely excellent function against harmful microorganisms, and have been widely used in the fields of medical and hygienic materials, biomaterials, and materials for daily necessities. Penkamei et al (chemical bulletin, 2016,74, 713-one 725) reviewed the research and application and development trends of guanidinium polymers at home and abroad, wherein the guanidinium polymers are important application directions in the field of high molecular materials.
Patents CN 1292397B, CN1350022, CN1351086, US 7,282,538B 2, EP 1486519B 1, special 2003-576488 and US 7,531,225B 2 disclose techniques of preparing functional master batches by bonding guanidinium polymers on general polyolefin molecular chains, and the obtained polyolefin master batches have functions of resisting harmful microorganisms, hydrophilic performance and antistatic performance; patent CN 1569923B discloses that guanidine salt polymer is bonded on general nylon and polyester molecular chain to prepare harmful microorganism resistant polyester and polyamide; patent CN 101210062B discloses the copolymerization of a guanidine salt polymer containing double bonds, unsaturated monomers and unsaturated hydrophilic compounds to prepare a hydrophilic polymer material resistant to harmful microorganisms; patent CN 101812160B provides a technique for preparing a functional masterbatch for resisting harmful microorganisms by bonding a biguanide salt polymer to a general polyolefin molecular chain; patent CN 101982202B discloses bonding guanidine salt polymer to the molecular chain of hydrogel to obtain highly safe hydrogel with harmful microorganism resistance; patent CN 103937003B discloses that guanidine salt polymer is prepared into block copolymer with different structures, forming a selectable structure with amphipathy or biocompatibility and strong resistance to harmful microorganisms, and bonding it to general polyolefin molecular chain; patent CN 104004139A provides a technique of applying guanidine salt polymer to low molecular wax.
The guanidine salt polymer used in the above patent shows a reaction characteristic of multifunctionality in the reaction process with epoxy group, isocyanate group, carboxylic acid or acid anhydride because both ends of the molecular chain are amine groups, and in this case, a cross-linking reaction is very easy to occur, which seriously affects the processing performance, mechanical property and harmful microorganism resistance of the finally obtained material. In this regard, patent CN106800652B discloses a technique of capping guanidine salt oligomer with a non-polar long-chain aliphatic monoamine structure to obtain a product of formula- (CH)2)4-18CH3Is a novel guanidine oligomer with a blocking structure, which can effectively reduce cross-linking reaction when being bonded with polymer.
However, because the reactivity of the long-chain aliphatic amine and the guanidine salt oligomer is lower, and meanwhile, the compatibility of the aliphatic chain and the guanidine salt polymer is poor, the efficiency of bonding and end capping is lower, a large amount of aliphatic amine which does not participate in the reaction can remain in the system and is difficult to separate, and adverse effects can be caused on the preparation and later-period use performance of the prepared harmful microorganism resistant material; in addition, the fatty amine has the defects of high corrosivity, high irritation, high toxicity and the like, and brings great potential safety hazard in the processing and using processes. Therefore, further research and innovation is needed in the capping technology of guanidinium polymers.
Disclosure of Invention
The present invention has been made to overcome the above problems occurring in the prior art, and an object of the present invention is to provide a novel guanidinium polymer and a method for preparing the same.
The technical solution of the invention is as follows:
a guanidinium polymer characterized in that the guanidinium polymer has a characteristic structure represented by formula 1:
wherein, Y1And Y2May be the same or different, and specifically is: cl-、Br-、HSO4 -、 HCO3 -、H2PO4 -、CH3COO-Or CH3(CH2)16COO-(ii) a m and n are natural numbers of 0-8, but m and n are not 0 at the same time; k is a natural number of 1-8; r1And R2The structure may be the same or different, and specifically contains one, two or more of the following functional groups:
r and R' are hydrogen or a structure containing at least one of the following characteristic functional groups; but R and R' are not both hydrogen:
the preparation method of the guanidine salt polymer is characterized by comprising the following steps:
(1) respectively adding Y defined in two reaction kettles1And Y2A guanidinium salt of the structure;
(2) selected structure as NH2-R1-NH2And NH2-R2-NH2The diamine with double terminal amino groups is respectively added into two reaction kettles for condensation polymerization according to the molar ratio of diamine to guanidine salt of 0.5-2.0, the reaction temperature is 80-180 ℃, and the reaction time is 0.5-10 hours;
(3) and combining the materials of the two reaction kettles into one reaction kettle, continuously reacting for 0.5-4.5 hours, then cooling to a temperature not higher than 160 ℃, adding an end-capping agent, wherein the addition amount of the end-capping agent is 1/10-1/2 of the total mole number of the guanidine salt, and continuously reacting. At this time, the condensation polymerization reaction and the end capping reaction are simultaneously performed, and the guanidine salt polymer shown in formula 1 is obtained after the reaction for 0.2 to 3 hours.
In the above preparation process, if Y1And Y2Same, R1And R2The same applies, and the preparation reaction can be carried out in the same reaction kettle.
The guanidine salt polymer can be used for carrying out grafting reaction with other various polymers to obtain a graft polymer containing the guanidine salt polymer, which has no crosslinking structure and good processability, such as: polyethylene grafted guanidinium polymer, polypropylene grafted guanidinium polymer, styrene-maleic anhydride copolymer grafted guanidinium polymer, styrene-acrylate-glycidyl methacrylate copolymer grafted guanidinium polymer, and the like.
The technical effects of the invention are shown as follows:
(1) the compound which has strong reactivity with amino and contains epoxy group, anhydride group or aldehyde group is selected as the end capping agent, so that the end capping rate can be improved, and the end capping reaction can be carried out under the relatively mild condition with relatively low temperature.
(2) Lower temperature conditions are beneficial to expand the selection range of the blocking agent, for example, the length of the fatty chain at the relatively inert end can be shortened, and the blocking agent with shorter fatty chain length is beneficial to increase the compatibility of the blocking agent and the guanidinium polymer, thereby further improving the efficiency of the blocking reaction and increasing the blocking rate.
(3) The selection range of the blocking agent is expanded, so that the blocking agent with low corrosivity, low irritation, low toxicity and relatively higher safety is favorably selected, for example, butyl glycidyl ether is a commonly used reactive diluent of epoxy resin and has low toxicity and low harm, and the butyl glycidyl ether is selected as the blocking agent, so that the safety of the production process is favorably improved.
(4) The increase in the capping rate means that the content of residual capping agent in the capped guanidinium polymer product is reduced, which will significantly improve the quality of the capped guanidinium polymer product.
(5) The problems of low end capping efficiency, more monomer residues, high corrosivity, high irritation, high toxicity and the like of amine substances in the preparation process and the residual amine substances in the use process of the end capped guanidine salt polymer caused by the technology of end capping guanidine salt oligomer by adopting a nonpolar long-chain aliphatic monoamine structure in the patent CN106800652B are solved.
(6) By adjusting and controlling the adding amount and the adding mode of the end capping agent, one side of the guanidine salt polymer is ensured to be capped instead of two sides, the capability of the capped guanidine salt polymer participating in subsequent reactions, such as grafting reaction, is ensured, and a cross-linking structure is avoided.
(7) By making a pair of Y1、Y2、R1、R2The four groups are selected, so that the obtained guanidine salt polymer has more flexible comprehensive performance, a larger selection space is provided for the guanidine salt polymer subjected to end capping at one side to participate in the subsequent grafting reaction, and the application value of the scheme is greatly improved.
Therefore, the novel preparation technology of the guanidine salt polymer provided by the invention overcomes the problems of low end-capping efficiency caused by end-capping by adopting long-chain aliphatic amine substances, high corrosivity, high irritation, high toxicity and the like of the long-chain aliphatic amine substances, and improves the safety of the preparation process; the residual quantity of the end-capping monomer in the prepared guanidine salt polymer is less, so that the guanidine salt polymer has better product safety and improves the product quality; the prepared guanidine salt polymer has reduced reaction functionality, so that the defect that the guanidine salt polymer with multiple functionality is easy to generate cross-linking in the bonding reaction process with the polymer in the prior art is avoided, and the product quality of the subsequently produced graft polymer is improved.
Detailed Description
The invention provides a novel preparation technology of a guanidinium polymer, aiming at the problems that the prior art has technical defects in the end capping process of the guanidinium polymer, and further causes various defects in subsequent application of the guanidinium polymer.
The technology is embodied by a novel guanidine salt polymer, and the characteristic structure of the polymer is as follows:
wherein, Y1And Y2May be the same or different, and specifically is: cl-、Br-、HSO4 -、 HCO3 -、H2PO4 -、CH3COO-Or CH3(CH2)16COO-；
m and n are natural numbers of 0-8, but m and n are not 0 at the same time; k is a natural number of 1-8;
R1and R2The structure may be the same or different, and specifically, the structure may contain one, two or more of the following functional groups:
r and R 'are hydrogen, or a structure containing at least one of the following characteristic functional groups, but R and R' are not both hydrogen:
when in preparation, HCl, HBr and H are directly or indirectly selected2SO4、H2CO3Acetic acid, H3PO4Or stearic acid, or their corresponding salts (such as ammonium chloride, ammonium dihydrogen phosphate, etc.), with dicyandiamide or guanidine compounds to obtain guanidine salt with definite acid ion shown in formula 2;
then, selecting the structure as NH2-R1-NH2And NH2-R2-NH2The diamine with double amino groups and the guanidine salt are subjected to polycondensation reaction;
and finally, carrying out end capping reaction by adopting an end capping agent with one end capable of reacting with amino and the other end relatively inert, thereby preparing the guanidine salt polymer.
Specifically, the preparation process mainly comprises the following three steps:
(1) separately adding Y defined by formula 2 into two reaction kettles1And Y2A guanidinium salt of the structure;
(2) selected structure as NH2-R1-NH2And NH2-R2-NH2The diamine with double terminal amino groups is respectively added into two reaction kettles for condensation polymerization according to the molar ratio of diamine to guanidine salt of 0.5-2.0, the reaction temperature is 80-180 ℃, and the reaction time is 0.5-10 hours;
(3) and combining the materials of the two reaction kettles into one reaction kettle, continuously reacting for 0.5-4.5 hours, then cooling to a temperature not higher than 160 ℃, adding an end-capping agent, wherein the addition amount of the end-capping agent is 1/10-1/2 of the total mole number of the guanidine salt, and continuously reacting. At this time, the condensation polymerization reaction and the end capping reaction are simultaneously performed, and the guanidine salt polymer shown in formula 1 is obtained after the reaction for 0.2 to 3 hours.
In the above preparation process, if Y1And Y2Same, R1And R2The same applies, and the preparation reaction can be carried out in the same reaction kettle.
According to the technical scheme of the invention, the Y of the guanidine salt can be selected in the step (1) according to different requirements1Structure and Y2And (5) structure. For example, in view of increasing the flame retardant properties of a guanidinium polymer, a guanidinium salt of a phosphate structure may be selected; considering the reduction of corrosiveness to ferrous materials, the content of chloride ions can be reduced or guanidine salts without chloride ions can be selected; the CH-containing polymer may be selected in consideration of lowering the viscosity of the guanidinium polymer3(CH2)16COO-A guanidinium salt of the structure; HCO-containing polymers may be selected for better degradability of the guanidinium polymer3 -Or CH3COO-A guanidinium salt of the structure; y of different structure1And Y2The combination is more beneficial to adjusting the comprehensive performance of the guanidine salt polymer.
Diamine and guanidine salt in the step (2)The molar ratio of (a) to (b) is 0.5 to 2.0, preferably 0.8 to 1.2, and more preferably 0.95 to 1.05, so as to obtain a guanidinium polymer having a relatively high molecular weight after condensation polymerization. Said R1And R2The structures of (a) may be the same or different.
The blocking agent in step (3) is a compound that can react with amine group at one end and is relatively inert at the other end, and includes but is not limited to: monoepoxy group-containing compounds such as butyl glycidyl ether, octyl glycidyl ether, dodecyl glycidyl ether; acid anhydride compounds such as phthalic anhydride, succinic anhydride; aldehyde compounds, such as benzaldehyde, phenylacetaldehyde, lauraldehyde and ligustral.
The blocking reaction between the blocking agent and the guanidinium polymer in step (3) may result in both ends of the guanidinium polymer being blocked. If both ends are capped, the terminal functional group is lacking to participate in the subsequent reaction, resulting in a weakened subsequent reaction capability. Therefore, in order to obtain a reaction product with one end blocked as much as possible, the blocking agent is introduced in a slow dropwise manner or a manner of gradually adding in batches, and the aim of one end blocking is achieved as much as possible through the reaction condition that the concentration of the end group of the guanidinium polymer is far greater than that of the blocking agent.
When the end capping agent is butyl glycidyl ether, the end capping reaction process is as follows:
when the end capping agent is phthalic anhydride, the end capping reaction process is as follows:
when the end capping agent is benzaldehyde, the end capping reaction process is as follows:
the guanidine salt polymer can be used for carrying out grafting reaction with other various polymers to obtain a graft polymer containing the guanidine salt polymer. Such as:
1) reacting with polyethylene grafted maleic anhydride or polyethylene grafted glycidyl methacrylate to prepare a polyethylene grafted guanidine salt polymer;
2) reacting with polypropylene grafted maleic anhydride or polypropylene grafted glycidyl methacrylate to prepare polypropylene grafted guanidinium polymer;
3) reacting with a styrene-maleic anhydride copolymer to prepare a styrene-maleic anhydride copolymer grafted guanidinium polymer;
4) reacting with styrene-acrylate-glycidyl methacrylate copolymer to obtain styrene-acrylate-glycidyl methacrylate copolymer grafted guanidinium salt polymer.
The graft polymer obtained has a similar structure as follows:
in contrast, if non-end-capped guanidinium polymers are used, a crosslinked structure is obtained which resembles a segment which would drastically reduce the processability of the graft polymer or even render it impossible to process it at all.
The technical scheme of the invention is further illustrated by the following specific examples. It should be noted that the illustrated embodiments are merely exemplary of the technical solutions of the present invention, and any technical solution formed by adopting equivalent substitution or equivalent transformation falls within the scope of the present invention.
[ example 1 ]
38.2g of guanidine hydrochloride (0.4mol) and 62.8g of guanidine phosphate (0.4mol) were taken and charged into two three-necked flasks, respectively. Then, 54.5g of m-xylylenediamine (0.4mol) was added to the guanidine hydrochloride-containing flask, and 46.5g of 1, 6-hexanediamine (0.4mol) was added to the guanidine hydrochloride-containing flask, and the mixture was stirred and heated to 90 ℃ under nitrogen atmosphere to react for 2.5 hours. The contents of both flasks were then combined in one flask and the reaction was continued for 2 hours with gradual warming to 170 ℃. Finally, the temperature was lowered to 158 ℃, 38.8g of dodecyl glycidyl ether (0.16mol) was added dropwise over 1.5 hours, and then the reaction was carried out for 0.5 hour, and the mixture was poured out while it was hot to obtain guanidinium polymer-1.
[ example 2 ]
62.8g of guanidine phosphate (0.4mol) and 68.7g of guanidine stearate (0.2mol) were taken and charged into two three-necked flasks, respectively. Then 54.5g of m-xylylenediamine (0.4mol) was added to the guanidine phosphate-containing flask, and 23.2g of 1, 6-hexanediamine (0.2mol) was added to the guanidine stearate-containing flask, and the mixture was stirred and heated to 105 ℃ under nitrogen atmosphere for 2 hours. The contents of both flasks were then combined in one flask and the reaction was continued for 3 hours with gradual warming to 175 ℃. Finally, the temperature was lowered to 155 ℃ and 4 times in 1 hour, and 14.8g in total of phthalic anhydride (0.1mol) was added, followed by reaction for another 0.5 hour and pouring out while hot to obtain guanidinium polymer-2.
[ example 3 ]
48.4g of guanidine carbonate (0.4mol) and 137.4g of guanidine stearate (0.4mol) were taken and charged into two three-necked flasks, respectively. Then, 40.8g of pentamethylenediamine (0.4mol) was added to the guanidine carbonate-containing flask, and 40.8g of pentamethylenediamine (0.4mol) was also added to the guanidine stearate-containing flask, and the mixture was stirred and heated to 95 ℃ under nitrogen atmosphere to react for 1.5 hours. The contents of both flasks were then combined in one flask and the reaction was continued for 3 hours with gradual warming to 170 ℃. Finally, the temperature was lowered to 150 ℃, 26g of butyl glycidyl ether (0.2mol) was added dropwise over 1.5 hours, and then the reaction was carried out for another 0.5 hour, and the mixture was poured out while it was hot to obtain guanidinium polymer-3.
[ example 4 ]
38.2g of guanidine hydrochloride (0.4mol) are added into a three-neck flask, then 46.4g of 1, 6-hexamethylene diamine (0.4mol) are added, stirred and heated to 90 ℃ under the protection of nitrogen, and reacted for 1.5 hours. The reaction was then continued for 4 hours with gradual warming to 175 ℃. Finally, the temperature was lowered to 158 ℃, 10.5g of butyl glycidyl ether (0.08mol) was added dropwise over 1.5 hours, and then the reaction was further carried out for 0.5 hour, and the mixture was poured out while it was hot to obtain guanidinium polymer-4.
[ example 5 ]
38.2g of guanidine hydrochloride (0.4mol) is added into a three-neck flask, then 58.4g of triethylene tetramine (0.4mol) is added, and the mixture is stirred and heated to 85 ℃ under the protection of nitrogen to react for 1.5 hours. The reaction was then continued for 3 hours with gradual warming to 165 ℃. Finally, the temperature is reduced to 150 ℃, 10g (0.094mol) of benzaldehyde is dripped in 1 hour, then the reaction is carried out for 25 minutes, and the solution is poured out when the solution is hot, so that the guanidine salt polymer-5 is obtained.
[ example 6 ]
38.2g of guanidine hydrochloride (0.4mol) were taken in a three-necked flask, and 62.2g of 1, 8-diamino-3, 6-dioxaoctane (0.42mol) was added thereto, and the mixture was stirred and heated to 90 ℃ under nitrogen protection to react for 1.0 hour. The reaction was then continued for 4 hours with gradual warming to 170 ℃. Finally, the temperature was lowered to 150 ℃, 12g of butyl glycidyl ether (0.092mol) was added dropwise over 1.5 hours, and then the reaction was further carried out for 35 minutes, and the solution was poured out while it was hot to obtain guanidinium polymer-6.
[ example 7 ]
62.8g of guanidine phosphate (0.4mol) was taken in a three-necked flask, and then 48.0g of 1, 3-cyclohexane diamine (0.42mol) was added thereto, stirred and heated to 100 ℃ under nitrogen protection, and reacted for 1.5 hours. The reaction was then continued for 3 hours with gradual warming to 170 ℃. Finally, the temperature was reduced to 155 ℃, 16g of octyl glycidyl ether (0.086mol) was added dropwise over 1.5 hours to react, and then, after 35 minutes, the mixture was poured out while hot to obtain guanidinium polymer-7.
[ COMPARATIVE EXAMPLE 1 ] (COMPARATIVE WITH EXAMPLE 2)
62.8g of guanidine phosphate (0.4mol) and 68.7g of guanidine stearate (0.2mol) were taken and charged into two three-necked flasks, respectively. Then 54.5g of m-xylylenediamine (0.4mol) was added to the guanidine phosphate-containing flask, and 23.2g of 1, 6-hexanediamine (0.2mol) was added to the guanidine stearate-containing flask, and the mixture was stirred and heated to 105 ℃ under nitrogen atmosphere for 2 hours. The contents of both flasks were then combined in one flask and the reaction was continued for 3 hours with gradual warming to 175 ℃. Finally, 18.5g (0.1mol) of dodecylamine was added thereto and reacted for 2.0 hours, and the mixture was poured out while it was still hot to obtain a guanidinium polymer-p-1.
[ COMPARATIVE EXAMPLE 2 ] (COMPARATIVE WITH EXAMPLE 4)
38.2g of guanidine hydrochloride (0.4mol) are added into a three-neck flask, then 46.4g of 1, 6-hexamethylene diamine (0.4mol) are added, stirred and heated to 90 ℃ under the protection of nitrogen, and reacted for 1.5 hours. The reaction was then continued for 4 hours with gradual warming to 175 ℃. Finally, 14.9g of dodecylamine (0.08mol) was added to the reaction mixture to react for 2.0 hours, and the mixture was poured out while it was still hot to obtain a guanidinium polymer-p-2.
Table 1: capping ratio of each guanidinium polymer
[ application example 1 ]
10g of guanidine salt polymer-1, 40g of polypropylene grafted maleic anhydride (maleic anhydride grafting rate 2.0%) were mixed. Adding the mixture into a Haake internal mixer, and carrying out melt reaction for 6min at 180 ℃ to obtain the polypropylene grafted guanidinium polymer-1.
[ application example 2 ]
6g of guanidine salt polymer, 4, 44g of polyethylene grafted maleic anhydride (maleic anhydride grafting rate: 1%), were mixed. Adding the mixture into a Haake internal mixer, and carrying out melt reaction for 6min at the temperature of 170 ℃ to obtain the polyethylene grafted guanidinium polymer-1.
[ application example 3 ]
10g of guanidinium polymer-4, 40g of styrene-maleic anhydride copolymer (maleic anhydride content: 5%) were mixed. Adding the mixture into a Haake internal mixer, and carrying out melt reaction for 6min at the temperature of 170 ℃ to obtain the styrene-maleic anhydride copolymer grafted guanidinium polymer-1.
[ application example 4 ]
10g of guanidinium polymer-4, 40g of styrene-acrylate-glycidyl methacrylate copolymer (glycidyl methacrylate content: 5%) were mixed. Adding the mixture into a Haake internal mixer, and carrying out melt reaction for 6min at 180 ℃ to obtain the styrene-acrylate-glycidyl methacrylate copolymer grafted guanidinium polymer-1.
In the application examples, the obtained guanidine salt graft polymer has good processing fluidity, is completely dissolved in a solvent, and has no cross-linking product. The grafting efficiency of the guanidine salt polymer is more than 93 percent.
[ application control example 1 ]
10g of an uncapped guanidine salt polymer and 40g of polypropylene-grafted maleic anhydride (maleic anhydride grafting rate: 2.0%) were mixed. Adding the mixture into a Haake internal mixer, and carrying out melt reaction for 6min at 180 ℃ to obtain the polypropylene grafted guanidinium polymer-2.
[ application control example 2 ]
6g of an uncapped guanidinium polymer and 44g of polyethylene-grafted maleic anhydride (maleic anhydride graft ratio: 1%) were mixed. Adding the mixture into a Haake internal mixer, and carrying out melt reaction for 6min at the temperature of 170 ℃ to obtain the polyethylene grafted guanidinium polymer-2.
[ application control example 3 ]
10g of an uncapped guanidinium polymer and 40g of a styrene-maleic anhydride copolymer (maleic anhydride content: 5%) were mixed. Adding the mixture into a Haake internal mixer, and carrying out melt reaction for 6min at the temperature of 170 ℃ to obtain the styrene-maleic anhydride copolymer grafted guanidinium polymer-2.
[ application control example 4 ]
10g of an uncapped guanidinium polymer and 40g of a styrene-acrylate-glycidyl methacrylate copolymer (glycidyl methacrylate content: 5%) were mixed. Adding the mixture into a Haake internal mixer, and carrying out melt reaction for 6min at 180 ℃ to obtain the styrene-acrylate-glycidyl methacrylate copolymer grafted guanidinium polymer-2.
In the above application control examples, severe crosslinking phenomenon was observed, and the reaction product was substantially not melt-flowable and was in a crosslinked powdery state. The comparison shows that the novel end capping technology disclosed by the invention greatly improves the end capping rate of the guanidine salt polymer and avoids the problems of processing difficulty, even crosslinking and the like caused by a polyfunctional reaction in subsequent use of the guanidine salt polymer.
Claims (10)
1. A guanidinium polymer characterized by: the guanidinium polymer has a characteristic structure represented by formula 1:
wherein, Y1And Y2Is Cl-, Br-, HSO4ˉ、HCO3ˉ、H2PO4ˉ、CH3COO-or CH3(CH2)16COO-which may be the same or different;
m and n are natural numbers of 0-8, but m and n are not 0 at the same time, and k is a natural number of 1-8;
R1and R2The structure of the functional group is one, two or more than two of the following functional groups, and the two functional groups may or may not be the same structure:
r and R 'are hydrogen, or a structure containing at least one of the following characteristic functional groups, but R and R' are not both hydrogen:
2. the method of preparing the guanidinium polymer of claim 1, comprising the steps of:
(1) respectively adding Y defined in the reaction kettle1And Y2A guanidinium salt of the structure;
(2) selected structure as NH2-R1-NH2And NH2-R2-NH2The diamine with double terminal amino groups is respectively mixed with the diamine containing Y according to the molar ratio of 0.5-2.0 to the guanidine salt1And Y2Guanidine salt of structureCondensation polymerization, wherein the reaction temperature is 80-180 ℃, and the reaction time is 0.5-10 hours;
(3) and (3) combining the materials reacted in the step (2), continuing to react for 0.5-4.5 hours, then cooling to a temperature not more than 160 ℃, adding a blocking agent, wherein the addition amount of the blocking agent is 1/10-1/2 of the total mole number of the guanidine salt, and continuing to react for 0.2-3 hours to obtain the guanidine salt polymer shown in the formula 1.
3. The method of preparing a guanidinium polymer of claim 2, wherein: y is1And Y2Same, R1And R2The same, the preparation process is carried out in the same reaction kettle.
4. The method of preparing a guanidinium polymer of claim 2, wherein: y is1And Y2R is1And R2If at least one group of structures are different, the step (1) and the step (2) are carried out in two reaction kettles, and the step (3) is carried out in one reaction kettle.
5. The method of preparing a guanidinium polymer of claim 2 or 3 or 4, wherein: before the step (1), HCl, HBr and H are directly or indirectly selected2SO4、H2CO3Acetic acid, H3PO4Or stearic acid, or their corresponding salts, with dicyandiamide or guanidine compounds to give a defined acid ion Y1And Y2A guanidinium salt of structure (la).
6. The method of preparing a guanidinium polymer of claim 2 or 3 or 4, wherein: the end-capping reagent in step (3) is a compound which can react with amine group at one end and is relatively inert at the other end.
7. The method of claim 6, wherein the guanidine salt polymer is prepared by: the end capping agent in the step (3) is butyl glycidyl ether, octyl glycidyl ether, dodecyl glycidyl ether, phthalic anhydride, succinic anhydride, benzaldehyde, phenylacetaldehyde, lauraldehyde or ligustral.
8. The method of preparing a guanidinium polymer of claim 2 or 3 or 4, wherein: and (4) introducing the end-capping reagent in the step (3) in a mode of slowly dripping or gradually adding in batches.
9. Use of a guanidinium polymer according to claim 1, characterized in that: the guanidine salt polymer and other polymers are subjected to grafting reaction to obtain the graft polymer containing the guanidine salt polymer with good processing performance.
10. Use of a guanidinium polymer according to claim 9, characterized in that:
carrying out grafting reaction on the guanidine salt polymer and polyethylene grafted maleic anhydride or polyethylene grafted glycidyl methacrylate to prepare a polyethylene grafted guanidine salt polymer;
or the guanidine salt polymer and polypropylene grafted maleic anhydride or polypropylene grafted glycidyl methacrylate are subjected to a grafting reaction to prepare a polypropylene grafted guanidine salt polymer;
or, the guanidine salt polymer reacts with styrene-maleic anhydride copolymer to prepare styrene-maleic anhydride copolymer grafted guanidine salt polymer;
or the guanidine salt polymer and the styrene-acrylate-glycidyl methacrylate copolymer are subjected to a grafting reaction to prepare the styrene-acrylate-glycidyl methacrylate copolymer grafted guanidine salt polymer.
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| CN114342950A (en) * | 2021-12-31 | 2022-04-15 | 上海明涌新材料有限公司 | Macromolecular guanidine salt disinfectant and preparation method and preparation thereof |
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| FR3060335B1 (en) * | 2016-12-21 | 2019-05-24 | L'oreal | CAPILLARY COMPOSITION COMPRISING GUANIDINE SALT, ALKANOLAMINE AND AMMONIUM HYDROXIDE AND CATIONIC AND / OR AMPHOTERIC POLYMERS |
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