Pre-crosslinked polymer and preparation method and application thereof, crosslinked polymer and preparation method and application thereof

Abstract

The invention relates to the field of high-molecular compounds, and discloses a pre-crosslinked polymer and a preparation method and application thereof, a crosslinked polymer and a preparation method and application thereof, the pre-crosslinked polymer comprises a polymer part A1, a polymer part A2 and a crosslinking group connecting the polymer part A1 and the polymer part A2, the polymer part A1 has a structure as shown in a formula (A1), the polymer part A2 has a structure as shown in a formula (A2), and the structures of the polymer part A1 and the polymer part A2 are the same or different; the cross-linking group has a structure as shown in a formula (B1) and / or a formula (B2), and the pre-crosslinked polymer has good water resistance after being heated and can be used for thermosetting plastic products. # imgabs0 #

Description

Technical Field

[0001] The present invention relates to the field of polymer compounds, and in particular to a pre-crosslinked polymer and a preparation method and application thereof, and a crosslinked polymer and a preparation method and application thereof. Background Art

[0002] Cross-linking and curing refers to the reaction of two or more linear molecules bonding and cross-linking to form a relatively stable molecule with a three-dimensional grid structure. Thermosetting plastics are plastics with thermosetting resin as the main component, and various additives are added to form products through the cross-linking and curing process. After the polymer is cross-linked and cured, its mechanical properties, thermal stability, wear resistance, solvent resistance and creep resistance are improved to varying degrees. Commonly used thermosetting plastics such as phenolic resin, urea-formaldehyde resin, and melamine resin are widely used in various fields such as heat-resistant materials, plywood adhesives, daily necessities, industrial products, and mechanical parts.

[0003] Anhydride copolymers carry highly active anhydride groups, among which the imide copolymers obtained by imidization modification have excellent thermal stability, water resistance and mechanical properties, and are very suitable as components of thermosetting plastics. The cross-linked polymers obtained by cross-linking the imide copolymers will greatly broaden their application areas, but there are currently few studies on the post-imide copolymer improvement. The traditional post-imide copolymer improvement method requires dissolving the anhydride copolymer in an organic solvent and then reacting with an amine reagent. The reaction product is often a linear copolymer with poor heat resistance, solvent resistance and water resistance. The use of organic solvents will pollute the environment and affect the downstream application of the product. Summary of the invention

[0004] The purpose of the present invention is to overcome the problem of poor water resistance of imide copolymers in the prior art, and to provide a pre-crosslinked polymer and a preparation method and application thereof, and a crosslinked polymer and a preparation method and application thereof.

[0005] In order to achieve the above-mentioned object, the first aspect of the present invention provides a pre-crosslinked polymer, wherein the pre-crosslinked polymer comprises a polymer portion A1, a polymer portion A2 and a crosslinking group connecting the polymer portion A1 and the polymer portion A2, the polymer portion A1 has a structure represented by formula (A1), the polymer portion A2 has a structure represented by formula (A2), and the structures of the polymer portion A1 and the polymer portion A2 are the same or different; the crosslinking group has a structure represented by formula (B1) and / or formula (B2),

[0006]

[0007]

[0008]

[0009]

[0010] Among them, X 1 , Y 1 , X 2 and Y 2 Each independently selected from hydroxyl or And X 1 With Y 1 At least one of X 2 and Y 2 At least one of

[0011] The R 1 , R 2 , R 3 , R 4 Each is independently selected from hydrogen, C1-C6 branched alkyl, aryl or C1-C6 straight chain alkyl; R 5 , R 6 , R 7 , R 8 Each is independently selected from hydrogen, C1-C4 branched alkyl or C1-C4 straight chain alkyl;

[0012] R 9 Selected from -O-, C1-C6 branched alkylene, C1-C6 straight chain alkylene, arylene or k is an integer from 0 to 8; R 10 A six-membered nitrogen heterocycle, a C1-C6 branched alkyl group, a C1-C6 straight-chain alkyl group or a C6-C15 alkenyl group;

[0013] m is an integer of 1-400, and n is an integer of 1-400.

[0014] The second aspect of the present invention provides a method for preparing a pre-crosslinked polymer, wherein the method comprises the following steps: contacting a polymer with a crosslinking agent in the presence of a solvent and an initiator to carry out a crosslinking reaction;

[0015] The polymer comprises polymer a1 and polymer a2; the polymer a1 has a structure represented by formula (a1), the polymer a2 has a structure represented by formula (a2), the structures of polymer a1 and polymer a2 are the same or different, and the cross-linking agent has a structure represented by formula (b1) and / or formula (b2);

[0016]

[0017]

[0018]

[0019]

[0020] Among them, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , m, and n are the same as those defined in any one of claims 1 to 3.

[0021] The third aspect of the present invention provides a pre-crosslinked polymer prepared by the method described in the second aspect of the present invention.

[0022] The fourth aspect of the present invention provides use of the pre-crosslinked polymers described in the first and third aspects of the present invention in thermosetting plastic products.

[0023] A fifth aspect of the present invention provides a cross-linked polymer, wherein the cross-linked polymer comprises a polymer having a structure represented by formula (z1) and / or a polymer having a structure represented by formula (z2).

[0024]

[0025]

[0026] Among them, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , m, and n are the same as those defined in any one of claims 1 to 3.

[0027] The sixth aspect of the present invention provides a method for preparing a cross-linked polymer, characterized in that the method comprises: heating the pre-cross-linked polymer described in the first aspect of the present invention or the third aspect of the present invention.

[0028] Alternatively, the pre-crosslinked polymer is prepared by the method described in the second aspect of the present invention, and then heated.

[0029] The seventh aspect of the present invention provides a cross-linked polymer prepared by the method described in the sixth aspect of the present invention.

[0030] The eighth aspect of the present invention provides use of the cross-linked polymer described in the seventh aspect of the present invention in a thermosetting plastic product.

[0031] Through the above technical scheme, the pre-crosslinked polymer provided by the present invention can obtain a cross-linked polymer with strong water resistance after heating, and the pre-crosslinked polymer and the cross-linked polymer can be applied to thermosetting plastic products, such as highly transparent thermosetting plastic products, adhesives, and water-resistant and heat-resistant coatings.

[0032] The method for preparing the pre-crosslinked polymer and the crosslinked polymer provided by the present invention does not use organic solvents, is not likely to cause environmental pollution, and is not likely to affect the downstream applications of the pre-crosslinked polymer and the crosslinked polymer.

[0033] The preparation method of the pre-crosslinked polymer and the crosslinked polymer of the present invention is simple, has strong operability, has low equipment requirements, and is suitable for industrial production.

[0034] In the preparation method of the pre-crosslinked polymer and the crosslinked polymer provided by the present invention, the raw materials are widely available and cheap, and the cost is low. DETAILED DESCRIPTION

[0035] The endpoints and any values ​​of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

[0036] In the present invention, the heating refers to heating at a temperature above 100 degrees Celsius.

[0037] A first aspect of the present invention provides a pre-crosslinked polymer, wherein the pre-crosslinked polymer comprises a polymer portion A1, a polymer portion A2, and a crosslinking group connecting the polymer portion A1 and the polymer portion A2, the polymer portion A1 has a structure represented by formula (A1), the polymer portion A2 has a structure represented by formula (A2), and the structures of the polymer portion A1 and the polymer portion A2 are the same or different; the crosslinking group has a structure represented by formula (B1) and / or formula (B2),

[0038]

[0039]

[0040]

[0041]

[0042] Among them, X1 , Y 1 , X 2 and Y 2 Each independently selected from hydroxyl or And X 1 With Y 1 At least one of X 2 and Y 2 At least one of

[0043] R 1 , R 2 , R 3 , R 4 Each is independently selected from hydrogen, C1-C6 branched alkyl, aryl or C1-C6 straight chain alkyl; R 5 , R 6 , R 7 , R 8 Each is independently selected from hydrogen, C1-C4 branched alkyl or C1-C4 straight chain alkyl;

[0044] R 9 Selected from -O-, C1-C6 branched alkylene, C1-C6 straight chain alkylene, arylene or k is an integer from 0 to 8; R 10 A six-membered nitrogen heterocycle, a C1-C6 branched alkyl group, a C1-C6 straight-chain alkyl group or a C6-C15 alkenyl group;

[0045] m is an integer of 1-400, and n is an integer of 1-400.

[0046] In the present invention, when the substituents of the polymer part A1, polymer part A2 and crosslinking group are selected from the above-mentioned specific groups, and m and n are the above-mentioned specific values, the pre-crosslinked polymer has strong water resistance after heating.

[0047] In the present invention, the wavy line represents the attachment site.

[0048] In the present invention, preferably, the R 1 , R 2 , R 3 , R 4 Each is independently selected from hydrogen, C1-C6 branched alkyl, C1-C6 straight chain alkyl, phenyl or phenyl substituted with C1-C6 alkyl.

[0049] More preferably, the R 1 , R 2 , R 3 , R 4 Each is independently selected from hydrogen, ethyl, propyl, isopropyl, n-butyl, isobutyl or phenyl.

[0050] In the present invention, preferably, the R 5 , R 6 , R 7 , R 8 Each is independently selected from hydrogen or C1-C4 straight chain alkyl.

[0051] In the present invention, more preferably, the R 5 , R 6 , R 7 , R 8 Each is independently selected from hydrogen, methyl or ethyl.

[0052] In the present invention, preferably, the R 9 Selected from ethylene, propylene, n-butylene, phenylene or k is an integer from 0 to 5.

[0053] In the present invention, preferably, the R 10 Selected from or

[0054] According to some preferred embodiments of the present invention, preferably, the pre-crosslinked polymer comprises a polymer portion A1, a polymer portion A2, and a crosslinking group connecting the polymer portion A1 and the polymer portion A2, wherein R 1 , R 2 , R 3 , R 4 Each is independently selected from hydrogen, C1-C6 branched alkyl, C1-C6 straight chain alkyl, phenyl or C1-C6 alkyl substituted phenyl, wherein R 5 , R 6 , R 7 , R 8 Each independently selected from hydrogen or C1-C4 straight chain alkyl, said R 9 Selected from ethylene, propylene, n-butylene, phenylene or k is an integer from 0 to 5, R 10 Selected from or m is an integer of 1-400, n is an integer of 1-400, when each substituent of polymer part A1, polymer part A2 and crosslinking group is selected from the above groups, and m and n are the above specific values, the pre-crosslinked polymer has stronger water resistance after heating.

[0055] According to some more preferred embodiments of the present invention, the pre-crosslinked polymer comprises a polymer portion A1, a polymer portion A2, and a crosslinking group connecting the polymer portion A1 and the polymer portion A2, wherein R 1 , R 2 , R 3 , R4 are each independently selected from hydrogen, ethyl, propyl, isopropyl, n-butyl, isobutyl or phenyl, wherein R 5 , R 6 , R 7 , R 8 Each independently selected from hydrogen, methyl or ethyl, said R 9 Selected from ethylene, propylene, n-butylene, phenylene or k is an integer from 0 to 5, R 10 Selected from or m is an integer of 1-400, n is an integer of 1-400, and when each substituent of polymer part A1, polymer part A2 and crosslinking group is selected from the above groups, and m and n are the above specific values, the water resistance of the pre-crosslinked polymer after heating is further enhanced.

[0056] In some preferred embodiments of the present invention, the pre-crosslinked polymer comprises at least one of a polymer having a structure represented by formula (y1), a polymer having a structure represented by formula (y2) or a polymer having a structure represented by formula (y3).

[0057]

[0058]

[0059]

[0060] The second aspect of the present invention provides a method for preparing a pre-crosslinked polymer, characterized in that the method comprises the following steps: contacting a polymer with a crosslinking agent in the presence of a solvent and an initiator to carry out a crosslinking reaction;

[0061] The polymer comprises polymer a1 and polymer a2; the polymer a1 has a structure represented by formula (a1), the polymer a2 has a structure represented by formula (a2), the structures of polymer a1 and polymer a2 are the same or different, and the cross-linking agent has a structure represented by formula (b1) and / or formula (b2);

[0062]

[0063]

[0064]

[0065]

[0066] Among them, R 1 , R 2 , R 3 , R 4 , R 5 , R6 , R 7 , R 8 , R 9 , R 10 , m, and n are the same as those defined in the pre-crosslinked polymer described in the first aspect of the present invention.

[0067] In the present invention, the method for preparing the pre-crosslinked polymer can make the prepared pre-crosslinked polymer have good water resistance after being heated.

[0068] According to some preferred embodiments of the present invention, the polymer a1 and polymer a2 can be independently selected from maleic anhydride polymer, citraconic anhydride polymer or dimethyl maleic anhydride polymer, for example, can be independently selected from maleic anhydride-styrene copolymer, maleic anhydride-n-butene copolymer or maleic anhydride-isobutylene copolymer, citraconic anhydride-styrene copolymer; the maleic anhydride polymer can be commercially available, and the maleic anhydride polymer, citraconic anhydride polymer or dimethyl maleic anhydride polymer can also be obtained by polymerization of at least one of maleic anhydride, citraconic anhydride, dimethyl maleic anhydride with at least one olefin having a carbon-carbon unsaturated double bond, for example, maleic anhydride, citraconic anhydride or dimethyl maleic anhydride can be copolymerized with at least one of styrene and C4-C8 olefins (such as n-butene, isobutylene). The number average molecular weight of the maleic anhydride-styrene copolymer is preferably 30000-80000 g / mol, and the mass percentage of the structural units provided by the maleic anhydride monomer is preferably 30-50%; the number average molecular weight of the maleic anhydride-n-butene copolymer is preferably 20000-60000 g / mol, and the mass percentage of the structural units provided by the maleic anhydride monomer is preferably 30-50%; the number average molecular weight of the maleic anhydride-isobutylene copolymer is preferably 20000-60000 g / mol, and the mass percentage of the structural units provided by the maleic anhydride monomer is preferably 30-50%; the number average molecular weight of the citraconic anhydride-styrene copolymer is preferably 30000-80000 g / mol, and the mass percentage of the structural units provided by the citraconic anhydride monomer is preferably 30-50%.

[0069] In the present invention, the crosslinking agent has multiple amination sites, which can react with the anhydride groups in the polymer, which is conducive to the polymer forming a three-dimensional network crosslinking structure. The conventional preparation method uses ammonia water as an amination agent, and starch (such as corn starch, cassava starch) provides polyols as a crosslinking agent, which is not conducive to the formation of a three-dimensional network crosslinking structure, and the water resistance of the obtained pre-crosslinked polymer after heating is poor. In addition, compared with the conventional preparation method, the preparation method of the present invention is simpler to operate.

[0070] According to a preferred embodiment of the present invention, the cross-linking agent is selected from urea and / or melamine.

[0071] In the present invention, the initiator is not particularly limited and is an initiator conventionally used in the art. In some preferred embodiments, the initiator is selected from at least one of alkali metal hydroxides, alkali metal carbonates and alkali metal bicarbonates.

[0072] In the present invention, preferably, the alkali metal hydroxide is selected from at least one of sodium hydroxide and potassium hydroxide.

[0073] In the present invention, preferably, the alkali metal carbonate is selected from at least one of sodium carbonate and potassium carbonate.

[0074] In the present invention, preferably, the alkali metal bicarbonate is selected from at least one of sodium bicarbonate and potassium bicarbonate.

[0075] In the present invention, preferably, the mass ratio of the polymer, the crosslinking agent and the initiator is 1:(0.05-2.5):(0.005-0.5), and when the mass ratio of the raw materials is in this range, the prepared pre-crosslinked polymer has good water resistance after heating. More preferably, the mass ratio of the polymer, the crosslinking agent and the initiator is 1:(0.1-1.5):(0.01-0.3), and when the mass ratio of the raw materials is in the above range, the prepared pre-crosslinked polymer has stronger water resistance after heating.

[0076] In the present invention, the preparation method may not use an organic solvent. In some preferred embodiments of the present invention, water may be used as a solvent. The preparation method is not likely to cause environmental pollution, is green and environmentally friendly, and is not likely to affect the downstream applications of the prepared pre-cross-linked polymer, and is even less likely to affect the downstream applications of the cross-linked polymer formed after the pre-cross-linked polymer is heated.

[0077] In the present invention, preferably, the amount of the solvent is 0.1-10 times the total mass of the polymer, crosslinking agent and initiator. In this range, the reaction can proceed normally. In order to make the viscosity of the reaction system moderate, more conducive to stirring, and more sufficient reaction, more preferably, the amount of the solvent is 0.5-5 times the total mass of the polymer, crosslinking agent and initiator.

[0078] In the present invention, when the polymer a1 is different from the polymer a2, the mass ratio of the polymer a1 to the polymer a2 is 1-5. When the ratio is within the above range, the water resistance of the prepared pre-cross-linked polymer after heating can be improved. In order to further improve the water resistance of the pre-cross-linked polymer after heating, preferably, the mass ratio of the polymer a1 to the polymer a2 is 1-2.

[0079] In the present invention, the contacting method may be to react at a temperature lower than the boiling point of the solvent, and the reaction time may be adjusted according to actual needs.

[0080] In some preferred embodiments of the present invention, the contacting method may be reacting at a temperature greater than 0° C. and less than 100° C. for 0.5-24 hours.

[0081] In the present invention, the contact temperature can be 10°C, 20°C, 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, 95°C, 98°C, 99°C, and any range consisting of any two of the above values, preferably 50-90°C.

[0082] In the present invention, the reaction time at a temperature greater than 0°C and less than 100°C can be 0.5h, 1h, 2h, 3h, 4h, 5h, 8h, 10h, 12h, 14h, 16h, 18h, 20h, 22h, 24h, and any range consisting of any two of the above values, preferably 0.5-5h.

[0083] In the present invention, preferably, the contacting method is to react at 50-90°C for 0.5-24h. The pre-cross-linked polymer prepared under the above conditions has better water resistance after heating. In order to further improve the water resistance of the pre-cross-linked polymer after heating, more preferably, the contacting method is to react at 50-90°C for 0.5-5h.

[0084] In some embodiments of the present invention, the pre-cross-linked polymer exists in an aqueous solution. At this time, the cross-linking degree of the pre-cross-linked polymer is low, the solubility of the pre-cross-linked polymer in water is good, and it will not obviously precipitate from the water. After heating, the cross-linked polymer can be obtained, and the cross-linked polymer has low solubility in water and can precipitate from the aqueous solution. After the aqueous solution evaporates, it is a transparent block solid.

[0085] According to a particularly preferred embodiment of the present invention, the preparation method of the cross-linked polymer comprises contacting a polymer and a cross-linking agent in the presence of a solvent and an initiator to carry out a cross-linking reaction; wherein R of the polymer a1 and the polymer a2 1 , R 2 , R 3 , R 4 are each independently selected from hydrogen, ethyl, propyl, isopropyl, n-butyl, isobutyl or phenyl, R 5 , R 6 , R 7 , R 8 Each is independently selected from hydrogen, methyl or ethyl, m is an integer of 1-400, and n is an integer of 1-400; the cross-linking agent is a compound of the structure shown in formula (b1), or a compound of the structure shown in formula (b2), R 9 Selected from ethylene, propylene, n-butylene, phenylene or k is an integer from 0 to 5, R 10 Selected from or The solvent is water; the initiator is at least one of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate and potassium bicarbonate; the mass ratio of the polymer, the crosslinking agent and the initiator is 1:(0.1-1.5):(0.01-0.3); the amount of the solvent is 0.5-5 times the total mass of the polymer, the crosslinking agent and the initiator; the mass ratio of the polymer a1 to the polymer a2 is 1-2; the contact method is: reacting at 50-90°C for 0.5-5h and then heating at 100-200°C for 0.2-6h. The above preparation method can further improve the water resistance of the prepared pre-crosslinked polymer after heating.

[0086] The third aspect of the present invention provides a pre-crosslinked polymer prepared by the method described in the second aspect of the present invention.

[0087] The fourth aspect of the present invention provides use of the pre-crosslinked polymer described in the first aspect and the third aspect of the present invention in a thermosetting plastic product.

[0088] In the present invention, the thermosetting plastic product may be a highly transparent thermosetting plastic product, an adhesive, or a water-resistant and heat-resistant coating.

[0089] The pre-crosslinked polymer of the present invention can be used by uniformly coating a 10 wt % to 60 wt % aqueous solution of the pre-crosslinked polymer on a substrate or pouring it into a mold of a fixed shape, followed by heating to obtain a finished product.

[0090] A fifth aspect of the present invention provides a cross-linked polymer, wherein the cross-linked polymer comprises a polymer having a structure represented by formula (z1) and / or a polymer having a structure represented by formula (z2);

[0091]

[0092]

[0093] Among them, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , m, and n are the same as those defined in the pre-crosslinked polymer described in the first aspect of the present invention.

[0094] The cross-linked polymer provided by the invention has good water resistance.

[0095] The sixth aspect of the present invention provides a method for preparing a cross-linked polymer, wherein the method comprises: heating the pre-cross-linked polymer described in the first aspect of the present invention or the third aspect of the present invention;

[0096] Alternatively, the pre-crosslinked polymer is prepared by the method described in the second aspect of the present invention, and then heated.

[0097] In the present invention, the heating temperature may be such that the crosslinking degree of the pre-crosslinked polymer is increased and / or the solvent (eg, water) in the pre-crosslinked polymer reaction system is removed.

[0098] In the present invention, preferably, the heating temperature is above 100°C. In order to reduce production energy consumption and control production costs, the heating temperature is more preferably 100-200°C. For example, it can be 100°C, 110°C, 120°C, 130°C, 140°C, 150°C, 160°C, 170°C, 180°C, 190°C, 200°C and any range consisting of any two of the values.

[0099] In the present invention, the heating time is not particularly limited. In the present invention, the heating temperature can increase the crosslinking degree of the pre-crosslinked polymer and / or remove the solvent (such as water) in the pre-crosslinked polymer reaction system. For example, the heating time can be 0.2-6h, preferably 0.5-3h.

[0100] In some embodiments of the present invention, the pre-cross-linked polymer exists in an aqueous solution. At this time, the cross-linking degree of the pre-cross-linked polymer is low, the solubility of the pre-cross-linked polymer in water is good, and it will not obviously precipitate from the water. After heating, the cross-linked polymer can be obtained, and the cross-linked polymer has low solubility in water and can precipitate from the aqueous solution. After the aqueous solution evaporates, it is a transparent block solid.

[0101] The seventh aspect of the present invention provides a cross-linked polymer prepared by the method described in the sixth aspect of the present invention.

[0102] The eighth aspect of the present invention provides use of the cross-linked polymer described in the seventh aspect of the present invention in a thermosetting plastic product.

[0103] In the present invention, the thermosetting plastic product may be a highly transparent thermosetting plastic product, an adhesive, or a water-resistant and heat-resistant coating.

[0104] The cross-linked polymer of the present invention can be used by uniformly coating a pre-cross-linked polymer (the pre-cross-linked polymer can be present in an aqueous solution, and the content of the pre-cross-linked polymer can be 10 wt %-60 wt %) for preparing the cross-linked polymer on a substrate or pouring it into a mold of a fixed shape, followed by heating to obtain a finished product containing the cross-linked polymer.

[0105] The present invention will be described in detail below through examples.

[0106] The reagents or instruments used without indicating the manufacturer are all conventional products that can be obtained through commercial channels.

[0107] The raw materials and reagents used in the preparation examples, embodiments and comparative examples were purchased from Sinopharm Chemical Reagent Co., Ltd.

[0108] Preparatory Example 1

[0109] This preliminary example is used to illustrate the maleic anhydride-styrene copolymer used in the present invention and its preparation method.

[0110] 18.2 g of styrene and 17.2 g of maleic anhydride were dissolved in 500 ml of isoamyl acetate, and 200 mg of azobisisobutyronitrile was added, and the mixture was reacted at 70° C. for 6 hours. After the reaction, the product was centrifuged at a speed of 7000 r / min for 10 minutes, and hexane was added, and the product was washed and centrifuged three times, and vacuum dried to constant weight to obtain a maleic anhydride-styrene copolymer.

[0111] The number average molecular weight of the maleic anhydride-styrene copolymer is 50,000 g / mol, and the mass percentage of the structural unit provided by the maleic anhydride monomer is 40%.

[0112] Preparatory Example 2

[0113] This preliminary example is used to illustrate the maleic anhydride-n-butene copolymer used in the present invention and its preparation method.

[0114] 31.4 g of maleic anhydride was dissolved in 500 ml of isoamyl acetate, and 200 mg of azobisisobutyronitrile was added, and the mixture was added into a 2 L high pressure reactor, which was sealed and filled with 18.0 g of n-butene, and reacted at 70° C. for 6 hours. After the reaction, the product was centrifuged at a speed of 7000 r / min for 10 minutes, and hexane was added, and the product was washed and centrifuged three times repeatedly, and vacuum dried to constant weight to obtain a maleic anhydride-n-butene copolymer.

[0115] The number average molecular weight of the maleic anhydride-n-butene copolymer is 30,000 g / mol, and the mass percentage of the structural unit provided by the maleic anhydride monomer is 35%.

[0116] Preparatory Example 3

[0117] This preliminary example is used to illustrate the maleic anhydride-isobutylene copolymer used in the present invention and its preparation method.

[0118] 31.4 g of maleic anhydride was dissolved in 500 ml of isoamyl acetate, and 200 mg of azobisisobutyronitrile was added, and the mixture was added into a 2 L high pressure reactor, which was sealed and filled with 18.0 g of isobutylene, and reacted at 70° C. for 6 hours. After the reaction, the product was centrifuged at a speed of 7000 r / min for 10 minutes, and hexane was added, and the product was washed and centrifuged three times, and vacuum dried to constant weight to obtain a maleic anhydride-n-butene copolymer.

[0119] The number average molecular weight of the maleic anhydride-isobutylene copolymer is 51000 g / mol, and the mass percentage of the structural unit provided by the maleic anhydride monomer is 45%.

[0120] Preparatory Example 4

[0121] This preliminary example is used to illustrate the citraconic anhydride-styrene copolymer used in the present invention and its preparation method.

[0122] 18.2 g of styrene and 19.7 g of maleic anhydride were dissolved in 500 ml of isoamyl acetate, and 200 mg of azobisisobutyronitrile was added, and the mixture was reacted at 70° C. for 6 hours. After the reaction, the product was centrifuged at a speed of 7000 r / min for 10 minutes, and hexane was added, and the product was washed and centrifuged three times, and vacuum dried to constant weight to obtain a citraconic anhydride-styrene copolymer.

[0123] The number average molecular weight of the citraconic anhydride-styrene copolymer is 45000 g / mol, and the mass percentage of the structural unit provided by the citraconic anhydride monomer is 38%.

[0124] Example 1

[0125] Weigh the reaction raw materials, each 100g of which contains the following components in mass percentage: 20% maleic anhydride-styrene copolymer, 2% urea, 0.2% sodium hydroxide, and the rest water. After the raw materials are mixed evenly, stir at 80°C for 2h to form a viscous solution to obtain a pre-crosslinked polymer Y1, and heat at 100°C for 3h to obtain a crosslinked polymer.

[0126] Example 2

[0127] The reaction raw materials were weighed, and each 100 g contained the following components in mass percentage: 50% maleic anhydride-styrene copolymer, 5% urea, 0.5% sodium hydroxide, and the rest water. After the raw materials were mixed evenly, they were stirred at 90° C. for 1 hour to form a viscous solution, and a pre-crosslinked polymer Y2 was obtained, and a crosslinked polymer was obtained after heating at 120° C. for 1 hour.

[0128] Example 3

[0129] The reaction raw materials were weighed, and each 100 g contained the following components in mass percentage: 25% maleic anhydride-styrene copolymer, 25% urea, 5% sodium hydroxide, and the rest was water. After the raw materials were mixed evenly, they were stirred at 60° C. for 3 h to form a viscous solution, and a pre-crosslinked polymer Y3 was obtained, which was then heated at 150° C. for 1 h to obtain a crosslinked polymer.

[0130] Example 4

[0131] The reaction raw materials were weighed, and each 100 g contained the following components in mass percentage: 20% maleic anhydride-styrene copolymer, 25% urea, 5% sodium hydroxide, and the rest was water. After the raw materials were mixed evenly, they were stirred at 60° C. for 3 h to form a viscous solution, and a pre-crosslinked polymer Y4 was obtained, and a crosslinked polymer was obtained after heating at 120° C. for 3 h.

[0132] Example 5

[0133] The reaction raw materials were weighed, and each 100 g contained the following components in mass percentage: 50% maleic anhydride-styrene copolymer, 5% urea, 0.5% potassium hydroxide, and the rest was water. After the raw materials were mixed evenly, they were stirred at 90° C. for 1 hour to form a viscous solution to obtain a pre-crosslinked polymer Y5, and then heated at 120° C. for 3 hours to obtain a crosslinked polymer.

[0134] Example 6

[0135] The reaction raw materials were weighed, and each 100 g contained the following components in mass percentage: 50% maleic anhydride-styrene copolymer, 5% urea, 0.5% potassium hydroxide, and the rest was water. After the raw materials were mixed evenly, they were stirred at 60° C. for 3 h to form a viscous solution, and a pre-crosslinked polymer Y6 was obtained, which was heated at 120° C. for 0.5 h to obtain a crosslinked polymer.

[0136] Example 7

[0137] The reaction raw materials were weighed, and each 100 g contained the following components in mass percentage: 25% maleic anhydride-styrene copolymer, 25% ethylenediamine, 5% sodium carbonate, and the rest was water. After the raw materials were mixed evenly, they were stirred at 90° C. for 2 hours to form a viscous solution, and a pre-crosslinked polymer Y7 was obtained, and a crosslinked polymer was obtained after heating at 120° C. for 3 hours.

[0138] Example 8

[0139] The reaction raw materials were weighed, and each 100 g contained the following components in mass percentage: 25% maleic anhydride-styrene copolymer, 25% p-phenylenediamine, 5% potassium hydroxide, and the rest was water. After the raw materials were mixed evenly, they were stirred at 90° C. for 2 h to form a viscous solution, and a pre-crosslinked polymer Y8 was obtained, which was then heated at 120° C. for 3 h to obtain a crosslinked polymer.

[0140] Example 9

[0141] The reaction raw materials were weighed, and each 100 g contained the following components in mass percentage: 25% maleic anhydride-styrene copolymer, 25% melamine, 5% potassium hydroxide, and the rest was water. After the raw materials were mixed evenly, they were stirred at 90° C. for 2 hours to form a viscous solution to obtain a pre-crosslinked polymer Y9, and then heated at 120° C. for 3 hours to obtain a crosslinked polymer.

[0142] Example 10

[0143] Weigh the reaction raw materials, and each 100g contains the following components in mass percentage: 25% maleic anhydride-n-butene copolymer, 25% urea, 5% sodium hydroxide, and the rest is water. After the raw materials are mixed evenly, stir at 90°C for 1h to form a viscous solution to obtain a pre-crosslinked polymer Y10, and heat at 120°C for 3h to obtain a crosslinked polymer.

[0144] Embodiment 11

[0145] The reaction raw materials were weighed, and each 100 g contained the following components in mass percentage: 25% maleic anhydride-isobutylene copolymer, 25% urea, 5% sodium hydroxide, and the rest water. After the raw materials were mixed evenly, they were stirred at 90° C. for 1 h to form a viscous solution, and a pre-crosslinked polymer Y11 was obtained, and a crosslinked polymer was obtained after heating at 120° C. for 3 h.

[0146] Example 12

[0147] The reaction raw materials were weighed, and each 100 g contained the following components in mass percentage: 25% of citraconic anhydride-styrene copolymer, 25% of urea, 5% of sodium hydroxide, and the rest of water. After the raw materials were mixed evenly, they were stirred at 80° C. for 3 h to form a viscous solution, and a pre-crosslinked polymer Y12 was obtained, and a crosslinked polymer was obtained after heating at 150° C. for 3 h.

[0148] Embodiment 13

[0149] The reaction raw materials were weighed, and each 100 g contained the following components in mass percentage: 12.5% ​​maleic anhydride-styrene copolymer, 12.5% ​​maleic anhydride-isobutylene copolymer, 25% urea, 5% sodium hydroxide, and the rest was water. After the raw materials were mixed evenly, they were stirred at 60° C. for 3 h to form a viscous solution, and a pre-crosslinked polymer Y13 was obtained, and a crosslinked polymer was obtained after heating at 150° C. for 1 h.

[0150] Comparative Example 1

[0151] The reaction raw materials were weighed, and each 100 g contained the following components in mass percentage: 20% maleic anhydride-styrene copolymer, 15% ammonia water, 0.6% cassava starch, and the rest was water. After the raw materials were mixed evenly, they were stirred at 80° C. for 2 h to form a viscous solution to obtain a pre-crosslinked polymer YD1, and then heated at 100° C. for 3 h to obtain a crosslinked polymer.

[0152] Comparative Example 2

[0153] The reaction raw materials were weighed, and each 100 g contained the following components in mass percentage: 20% maleic anhydride-styrene copolymer, 15% ammonia water, 0.6% corn starch, and the rest was water. After the raw materials were mixed evenly, they were stirred at 80°C for 2 hours to form a viscous solution to obtain a pre-crosslinked polymer YD2, and then heated at 100°C for 3 hours to obtain a crosslinked polymer.

[0154] Comparative Example 3

[0155] The reaction raw materials were weighed, and each 100 g contained the following components in mass percentage: 25% maleic anhydride-styrene copolymer, 25% hydroxymethyl urea, 5% sodium bicarbonate, and the rest was water. After the raw materials were mixed evenly, they were stirred at 90° C. for 2 h to form a viscous solution to obtain a pre-crosslinked polymer YD3, and then heated at 120° C. for 3 h to obtain a crosslinked polymer.

[0156] Comparative Example 4

[0157] The reaction raw materials were weighed, and each 100 g contained the following components in mass percentage: 25% maleic anhydride-styrene copolymer, 25% hydroxymethyl urea, 5% sodium hydroxide, and the rest was water. After the raw materials were mixed evenly, they were stirred at 60° C. for 3 h to form a viscous solution, and the pre-crosslinked polymer YD4 was obtained, and the crosslinked polymer was obtained after heating at 150° C. for 1 h.

[0158] Test Case

[0159] Water resistance test: Water resistance test: The cross-linked polymers obtained in the examples and comparative examples were immersed in deionized water, heated to 100°C until boiling, maintained for 2 hours, and observed whether the cross-linked polymer dissolved in the boiling water. Subsequently, the water was removed, and the cross-linked polymer was dried to obtain the cross-linked polymer, and the weight of the cross-linked polymer after cooking was weighed to calculate the weight loss ratio, wherein the weight loss ratio = [(the original weight of the cross-linked polymer - the weight of the cross-linked polymer after cooking) / the original weight of the cross-linked polymer] × 100%. The test results are shown in Table 1.

[0160] Table 1

[0161]

[0162]

[0163] It can be seen from the results in Table 1 that after heating the pre-crosslinked polymers Y1-Y13 provided in Examples 1-13, the water resistance of the obtained crosslinked polymers is better than that of the crosslinked polymers obtained by conventional means; when the crosslinking group R 9 and R 10 The carbonyl group, When heated, the cross-linked polymer obtained has better water resistance.

[0164] The pre-crosslinked polymers YD1 and YD2 obtained by conventional methods have worse water resistance after heating; the pre-crosslinked polymers YD3 and YD4 obtained by using hydroxymethyl urea as a crosslinking agent have worse water resistance than Examples 1-13 after heating.

[0165] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. A pre-crosslinked polymer, It is characterized in that The pre-crosslinked polymer comprises a polymer portion A1, a polymer portion A2, and a crosslinking group connecting the polymer portion A1 and the polymer portion A2, wherein the polymer portion A1 has a structure represented by formula (A1), the polymer portion A2 has a structure represented by formula (A2), and the structures of the polymer portion A1 and the polymer portion A2 are the same or different; and the crosslinking group has a structure represented by formula (B1) and / or formula (B2), Among them, X 1 , Y 1 , X 2 and Y 2 Each independently selected from hydroxyl or And X 1 With Y 1 At least one of R 1 , R 2 , R 3 , R 4 Each is independently selected from hydrogen, C1-C6 branched alkyl, aryl or C1-C6 straight chain alkyl; R 5 , R 6 , R 7 , R 8 Each is independently selected from hydrogen, C1-C4 branched alkyl or C1-C4 straight chain alkyl; R 9 Selected from -O-, C1-C6 branched alkylene, C1-C6 straight chain alkylene, arylene or k is an integer from 0 to 8; R 10 A six-membered nitrogen heterocycle, a C1-C6 branched alkyl group, a C1-C6 straight-chain alkyl group or a C6-C15 alkenyl group; m is an integer of 1-400, and n is an integer of 1-400.

2. The pre-crosslinked polymer according to claim 1, in, The R 1 , R 2 , R 3 , R 4 Each is independently selected from hydrogen, C1-C6 branched alkyl, C1-C6 straight chain alkyl, phenyl or C1-C6 alkyl substituted phenyl; Preferably, the R 1 , R 2 , R 3 , R 4 are each independently selected from hydrogen, ethyl, propyl, isopropyl, n-butyl, isobutyl or phenyl; Preferably, the R 5 , R 6 , R 7 , R 8 Each is independently selected from hydrogen or C1-C4 straight chain alkyl; More preferably, the R 5 , R 6 , R 7 , R 8 are each independently selected from hydrogen, methyl or ethyl; Preferably, the R 9 Selected from ethylene, propylene, n-butylene, phenylene or k is an integer from 0 to 5; Preferably, the R 10 Selected from 3. The pre-crosslinked polymer according to claim 1 or 2, in, The pre-crosslinked polymer comprises at least one of a polymer having a structure represented by formula (y1), a polymer having a structure represented by formula (y2) or a polymer having a structure represented by formula (y3).

4. A method for preparing a pre-crosslinked polymer, It is characterized in that The method comprises the following steps: in the presence of a solvent and an initiator, contacting a polymer with a crosslinking agent to carry out a crosslinking reaction; The polymer comprises polymer a1 and polymer a2; the polymer a1 has a structure represented by formula (a1), the polymer a2 has a structure represented by formula (a2), the structures of polymer a1 and polymer a2 are the same or different, and the cross-linking agent has a structure represented by formula (b1) and / or formula (b2); Among them, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , m, and n are the same as those defined in any one of claims 1 to 3.

5. The method according to claim 4, in, The initiator is selected from at least one of alkali metal hydroxides, alkali metal carbonates and alkali metal bicarbonates; and / or, the solvent is water; Preferably, the alkali metal hydroxide is selected from at least one of sodium hydroxide and potassium hydroxide; Preferably, the alkali metal carbonate is selected from at least one of sodium carbonate and potassium carbonate; Preferably, the alkali metal bicarbonate is selected from at least one of sodium bicarbonate and potassium bicarbonate.

6. The method according to claim 4 or 5, in, The mass ratio of the polymer, the crosslinking agent and the initiator is 1:(0.05-2.5):(0.005-0.5), preferably 1:(0.1-1.5):(0.01-0.3); And / or, the amount of the solvent used is 0.1-10 times, preferably 0.5-5 times, the total mass of the polymer, the crosslinking agent and the initiator.

7. The method according to claim 4 or 5, in, The polymer a1 is different from the polymer a2, and the mass ratio of the polymer a1 to the polymer a2 is 1-5, preferably 1-2.

8. The method according to claim 4 or 5, in, The contacting method is: reacting at 50-90° C. for 0.5-24 hours; Preferably, the contact time is 0.5-5h.

9. A pre-crosslinked polymer prepared by the method according to any one of claims 4 to 8.

10. Use of the pre-crosslinked polymer according to any one of claims 1 to 3 and 9 in thermosetting plastic products.

11. A cross-linked polymer, It is characterized in that The cross-linked polymer comprises a polymer having a structure represented by formula (z1) and / or a polymer having a structure represented by formula (z2); Among them, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , m, and n are the same as those defined in any one of claims 1 to 3.

12. A method for preparing a cross-linked polymer, It is characterized in that The method comprises: heating the pre-crosslinked polymer according to any one of claims 1 to 3 or 9; Alternatively, the pre-crosslinked polymer is prepared according to the method of claims 4-8 and then heated.

13. The method according to claim 12, in, The heating temperature is above 100°C, preferably 100-200°C; Preferably, the heating time is 0.2-6h, preferably 0.5-3h.

14. A cross-linked polymer prepared by the method according to claim 12 or 13.

15. Use of the cross-linked polymer according to claim 11 or 14 in thermosetting plastic products.

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