Application of a surface modifier in polymer modification

Abstract

The present invention discloses an application of a surface modifier in polymer modification, wherein the molecular structure of the surface modifier comprises a lipophilic group and a hydrophilic group; wherein the lipophilic group comprises at least one functional group, and the functional group is selected from one or more of ‑H, alkyl, alkenyl, phenyl, aryl, cycloalkyl, cycloalkenyl and C≡C, etc.; the hydrophilic group comprises at least one functional group, and the functional group is selected from one or more of ‑H, ‑OH, alkoxy, aryl, aldehyde, carboxyl, ester, amino, cyano, nitro, halogen, anhydride, sulfoxide, epoxyalkyl, sulfonyl, sulfonamide, sulfamoyl and carbamoyl, etc. In this application, the addition amount of the surface modifier in the modification process of the polymer is small, the separation is simple, and no environmental pollution is caused; it has good temperature resistance, and the highest tolerable temperature is up to 350° C. At the same time, the polymer modified by the surface modifier has higher mechanical properties.

Description

Technical Field

[0001] The present invention relates to the technical field of fine chemicals and organic synthesis, and more specifically to the application of a surface modifier in polymer modification. Background Art

[0002] High molecular polymer surface modifier is a kind of substance with two functional groups of different properties. The biggest feature of its molecular structure is that it contains two groups with different chemical properties. One is an inorganic-friendly group that easily reacts chemically with the surface of inorganic substances; the other is an organic-friendly group that can react chemically with synthetic resins or other polymers or generate hydrogen bonds and dissolve in them to improve the interface between inorganic and organic substances, thereby greatly improving the performance of composite materials, such as physical properties, electrical properties, thermal properties, optical properties, etc. Surface modifiers are used in the rubber industry to improve the wear resistance and aging resistance of products such as tires, rubber sheets, rubber hoses, and rubber shoes.

[0003] The role of surface modifier in composite materials is that it can react with certain groups on the surface of the reinforcing material and with the matrix resin to form an interface layer between the reinforcing material and the resin matrix. The interface layer can transfer stress, thereby enhancing the bonding strength between the reinforcing material and the resin and improving the performance of the composite material. At the same time, it can also prevent other media from penetrating into the interface, improve the interface state, and is beneficial to the aging resistance, stress resistance and electrical insulation properties of the product. Summary of the invention

[0004] Based on the above problems, the purpose of the present invention is to provide an application of a surface modifier in polymer modification. In this application, the surface modifier is added in a small amount during the polymer modification process, is easy to separate, does not produce toxic and harmful gases, and does not cause environmental pollution; has good temperature resistance, and can withstand a maximum temperature of 350°C. At the same time, the polymer modified by the surface modifier has higher mechanical properties.

[0005] In order to achieve the above object, the present invention adopts the following technical solutions:

[0006] A surface modifier is used in polymer modification, wherein the surface modifier comprises a lipophilic group and a hydrophilic group in its molecular structure; wherein:

[0007] The lipophilic group contains at least one functional group, and the functional group is selected from one or more of -H, alkyl, alkenyl, phenyl, aryl, cycloalkyl, cycloalkenyl and C≡C;

[0008] The hydrophilic group contains at least one functional group, and the functional group is selected from one or more of -H, -OH, alkoxy, aryl, aldehyde, carboxyl, ester, amino, cyano, nitro, halide, anhydride, sulfoxide, epoxy, sulfonyl, sulfonamide, sulfamoyl and carbamoyl.

[0009] Preferably, the surface modifier is obtained by a semi-Diels-Alder reaction of a compound containing a C=C bond or a C≡C bond with an alkylene oxide, an alkane, an alkene, or maleic anhydride.

[0010] Preferably, the compound containing a C=C bond is selected from unsaturated fatty acids, olefins, and maleic anhydride.

[0011] Preferably, the olefin is selected from C5-C30 olefins.

[0012] Preferably, the olefin is selected from normal olefins or internal olefins.

[0013] Preferably, the internal olefin is selected from one or more of internal-hexene, internal-heptene, internal-octene, internal-nonene, internal-decene, internal-undecene, internal-dodecene, internal-tridecene, internal-tetradecene, internal-pentadecaene, internal-hexadecene, internal-heptadecaene, internal-octadecene, internal-nonadecaene and internal-eicosene.

[0014] Preferably, the normal olefin is selected from n-hexene.

[0015] Preferably, the unsaturated fatty acid is selected from oleic acid and cis-3-hexenoic acid.

[0016] Preferably, the compound comprising a C≡C bond is selected from n-hexyne.

[0017] Preferably, the alkylene oxide is selected from one or more of propylene oxide, butylene oxide and ethylene oxide.

[0018] Preferably, the alkane is selected from one or more of n-hexane, n-hexadecane, cyclohexane and n-dodecane.

[0019] Preferably, the olefin is selected from n-hexene or internal olefins.

[0020] Preferably, the molar ratio of the compound containing a C=C bond or a C≡C bond to the alkylene oxide, alkane, olefin, and maleic anhydride is 1:50 to 50:1, preferably 1:1 to 1:10, and more preferably 1:1 to 1:5.

[0021] Preferably, the reaction temperature is 150° C.-300° C. Exemplarily, the thermal reaction temperature includes, but is not limited to, 150° C.-250° C., 150° C.-180° C., 180° C.-200° C., 200° C.-220° C., 220° C.-250° C., and the like.

[0022] Preferably, in the reaction, after the temperature reaches 180°C, the temperature is raised to 200°C-250°C at a rate of 9°C-13°C per hour (preferably 10°C per hour).

[0023] Preferably, the reaction pressure is 100 kPa to 1000 kPa. Exemplarily, the reaction pressure includes, but is not limited to, 100 kPa to 200 kPa, 200 kPa to 400 kPa, 400 kPa to 600 kPa, 600 kPa to 800 kPa, 800 kPa to 1000 kPa.

[0024] Preferably, the reaction time is 5 h to 20 h. Exemplary reaction times include, but are not limited to, 5 h to 8 h, 8 h to 10 h, 10 h to 12 h, 12 h to 14 h, 14 h to 16 h, 16 h to 18 h, 18 h to 20 h, and the like.

[0025] Preferably, the reaction is carried out under stirring at a stirring rate of 50 to 500 rpm. Exemplarily, the stirring rate includes but is not limited to 50 to 150 rpm, 150 to 300 rpm, 300 to 400 rpm, 400 to 500 rpm, etc.

[0026] Preferably, the reaction is carried out under anaerobic conditions.

[0027] Preferably, the raw materials of the reaction further include an auxiliary agent, the auxiliary agent includes an effective ingredient, and the effective ingredient includes one or two of hydroquinone, potassium halide and methylhydroquinone; and / or

[0028] The active ingredient also contains 2,6-di-tert-butyl-p-cresol.

[0029] The auxiliary agent can be well used in the preparation of the surface modifier for polymer modification. The auxiliary agent has good catalytic activity for the preparation of the catalytic surface modifier, and the addition amount is small, the separation is simple, no toxic and harmful gas is generated, and no environmental pollution is caused; it has good temperature resistance, and the maximum tolerable temperature is 350°C; the auxiliary agent has good regeneration and reuse performance, and the number of times it can be reused in the generation reaction is more than 100 times. The purity of the surface modifier obtained by the present invention is not less than 99%, the reaction yield is more than 85%, and it has high production practicality.

[0030] Preferably, the catechol is selected from one of hydroquinone, catechol and resorcinol.

[0031] Preferably, the potassium halide is selected from potassium bromide or potassium iodide.

[0032] Preferably, the auxiliary agent further comprises a carrier, and the active ingredient is loaded on the carrier.

[0033] Preferably, the carrier is selected from one or more of alumina (such as α-Al2O3 or γ-Al2O3), silica, alumina-silica, titania, zeolite, kaolinite, clay, activated carbon, and silicon carbide.

[0034] Preferably, the carrier accounts for 0.1%-90% of the total weight of the auxiliary agent, preferably 0.1%-30%, more preferably 15%-25%.

[0035] Preferably, the auxiliary agent is solid or liquid. The auxiliary agent is preferably solid, and the solid microscopic surface is rough and has a larger specific surface area.

[0036] Preferably, the auxiliary agent has ≥5m 2 / g. More preferably, it has a BET surface area of ​​≥10m 2 / g BET surface area. Still more preferably, having 6m 2 / g-9m 2 / g BET surface area. BET surface area can be calculated by N2 physical adsorption analysis.

[0037] Preferably, the auxiliary agent has a pore volume of 0.1 ml / g-1.0 ml / g. More suitably, the auxiliary agent has a pore volume of 0.3 ml / g-0.8 ml / g. More suitably, the auxiliary agent has a pore volume of 0.3 ml / g-0.6 ml / g. The pore volume can be calculated using any suitable technique known in the art, such as, for example, the technique described in Fuel Processing Technology 135, 2015, 195-202.

[0038] Preferably, the molar ratio of the auxiliary agent to the total amount of reactants is 1:10 to 1:1000, preferably 1:10 to 1:100.

[0039] Preferably, the polymer is selected from plastic or rubber.

[0040] Preferably, the plastic is selected from one or more of polyvinyl chloride, polyethylene, polypropylene and polystyrene.

[0041] Preferably, the rubber is selected from one or more EPDM rubbers.

[0042] Preferably, the application comprises the following steps:

[0043] The surface modifier is mixed with a polymer and molded.

[0044] Preferably, the weight of the surface modifier is 0.1%-5% of the weight of the polymer.

[0045] In the present invention, "internal olefin" refers to "olefin with C=C at the internal position of the molecule".

[0046] In addition, unless otherwise specified, any range described in the present invention includes the end value and any numerical value between the end values ​​and any sub-range formed by the end value or any numerical value between the end values.

[0047] The beneficial effects of the present invention are as follows:

[0048] In the application provided in the present invention, when the surface modifier is used for the modification of polymers, especially in the modification of polyvinyl chloride, polyethylene, polypropylene, polystyrene, EPDM rubber, etc., the mechanical properties of the polymers can be greatly improved. BRIEF DESCRIPTION OF THE DRAWINGS

[0049] The specific implementation modes of the present invention are further described in detail below in conjunction with the accompanying drawings.

[0050] Figure 1 The UV-visible absorption spectrum of the surface modifier in Example 1 is shown.

[0051] Figure 2 The infrared absorption spectrum of the surface modifier in Example 1 is shown.

[0052] Figure 3 The appearance of the surface modifier additive prepared in Example 1 is shown.

[0053] Figure 4 The SEM image of the surface modifier combined with the polymer in Example 1 is shown.

[0054] Figure 5 The mechanical property test comparison of the polypropylene material after adding the surface modifier in Example 1 is shown. DETAILED DESCRIPTION

[0055] In order to more clearly illustrate the present invention, the present invention is further described below in conjunction with preferred embodiments and accompanying drawings. Similar components in the accompanying drawings are represented by the same reference numerals. It should be understood by those skilled in the art that the content specifically described below is illustrative rather than restrictive, and should not be used to limit the scope of protection of the present invention.

[0056] Some of the following embodiments include using olefins and alkylene oxides as raw materials, adding auxiliary agents, and synthesizing the target product surface modifier efficiently and selectively, and the specific reaction formula is:

[0057]

[0058] Wherein, in the above formula, R1 and R2 are straight-chain or branched alkyl groups, and the sum of the number of carbon atoms of R1 and R2 is 6-50.

[0059] The preparation of the surface modifier comprises the following steps: uniformly mixing mixed olefins and ethylene oxide, wherein the ethylene oxide and the olefins are mixed in a molar ratio of 1:1 to 4:1; then adding an auxiliary agent, wherein the ratio of the auxiliary agent to the total reactant is 1:10 to 1000; continuously stirring and heating, and rapidly heating to 180°C; then performing a catalytic reaction between 180°C and 250°C, and continuing for 10 to 20 hours; after the reaction is completed, filtering out the auxiliary agent, performing reduced pressure distillation on the solution, removing excess olefins (recovered for repeated use), and obtaining the surface modifier.

[0060] Some of the following embodiments include using olefins and maleic anhydride as raw materials, adding auxiliary agents, and synthesizing the target product with high efficiency and selectivity. The specific reaction formula is:

[0061]

[0062] Wherein, in the above formula, R1 and R2 are straight-chain or branched alkyl groups, and the sum of the number of carbon atoms of R1 and R2 is 6-50.

[0063] The preparation of the surface modifier comprises the following steps: uniformly mixing mixed olefins and maleic anhydride, wherein the maleic anhydride and the olefins are mixed in a molar ratio of 1:1-4; then adding an auxiliary agent, wherein the ratio of the auxiliary agent to the total reactant is 1:10-1000; continuously stirring and heating, and rapidly heating to 180°C; then performing a catalytic reaction between 180°C and 250°C, and continuing for 10-20 hours; after the reaction is completed, filtering out the auxiliary agent, performing reduced pressure distillation on the solution, removing excess olefins (recovered for repeated use), and obtaining the surface modifier.

[0064] Some of the following embodiments include using alkanes and maleic anhydride as raw materials, adding auxiliary agents, and synthesizing the target product with high efficiency and selectivity. The specific reaction formula is:

[0065] Wherein, in the above formula, R1 and R2 are straight-chain or branched alkyl groups, and the sum of the number of carbon atoms of R1 and R2 is 6-50.

[0066]

[0067] The preparation of the surface modifier comprises the following steps: uniformly mixing mixed alkanes and maleic anhydride, wherein the maleic anhydride and the alkanes are mixed in a molar ratio of 1:1-4; then adding an auxiliary agent, wherein the ratio of the auxiliary agent to the total reactant is 1:10-1000; continuously stirring and heating, and rapidly heating to 180°C; then performing a catalytic reaction at 180°C-250°C for 10-20 hours; after the reaction is completed, filtering out the auxiliary agent, performing reduced pressure distillation on the solution, removing excess alkanes (recovered for repeated use), and obtaining the surface modifier.

[0068] Example 1

[0069] A method for preparing a surface modifier comprises the following steps:

[0070] 40g of cyclohexene, 15.3g of propylene oxide and 1.90g of 2,6-di-tert-butyl-p-cresol supported on silica were weighed, all added to the reactor and mixed thoroughly, nitrogen was introduced to exhaust the air, the system pressure was 200kPa, the stirring speed was set to 200r / min, the temperature was gradually increased to 180℃, and then increased to 220℃ at a rate of 10℃ per hour, and the reaction was continued for 16h to obtain the desired surface modifier. The additive was recycled 20 times, and the conversion rate reached 88%. The color of the obtained surface modifier was light yellow.

[0071] Figure 1 The UV-visible absorption spectrum of the surface modifier in this example is shown. Figure 2 The infrared absorption spectrum of the surface modifier in this example is shown. -1 The stretching vibration peaks of methyl CH are on the left and right, 2800 cm -1 The CH stretching vibration peak of methylene is around 1900 cm -1 The stretching vibration peak of C=O is around 1800cm -1 is the stretching vibration peak of C=C, 1500cm -1 is the CH bending vibration peak, 1100cm -1 is the stretching vibration peak of CO, 900 cm -1 Nearby is the stretching vibration peak of =CH. Figure 3 The appearance of the surface modifier additive prepared in this example is shown. Figure 4 The SEM image of the surface modifier combined with the polymer in this embodiment shows that there is almost no space between the filler and the polymer material, and the modified appearance effect is significant. Figure 5 The comparison of mechanical properties test of the polypropylene material after adding the surface modifier in this embodiment is shown.

[0072] Example 2

[0073] A method for preparing a surface modifier comprises the following steps:

[0074] 40g of n-hexene, 15.3g of cis-3-hexenol and 0.95g of 2,6-di-tert-butyl-p-cresol were weighed and added to the reactor for thorough mixing. Nitrogen was introduced to exhaust the air. The system pressure was 200kPa, the stirring speed was set to 200r / min, the temperature was gradually increased to 180°C, and then increased to 220°C at a rate of 10°C per hour, and the reaction was continued for 16h to obtain a surface modifier, which was recycled for 20 times and the conversion rate reached 82%. The color of the obtained surface modifier was light yellow.

[0075] Example 3

[0076] A method for preparing a surface modifier comprises the following steps:

[0077] 40g of n-hexadecene, 15.3g of oxybutane and 3.80g of 2,6-di-tert-butyl-p-cresol supported on titanium dioxide were weighed, all added to the reactor and mixed thoroughly, nitrogen was introduced to exhaust the air, the system pressure was 200kPa, the stirring speed was set to 200r / min, the temperature was gradually increased to 180°C, and then increased to 220°C at a rate of 10°C per hour, and the reaction was continued for 16h to obtain a surface modifier, which was recycled 20 times and the conversion rate reached 84%. The color of the obtained surface modifier is light yellow.

[0078] Example 4

[0079] A method for preparing a surface modifier comprises the following steps:

[0080] 40g of dodecene, 15.3g of ethylene oxide and 1.90g of hydroquinone were weighed, all added to the reactor and mixed thoroughly, nitrogen was introduced to exhaust the air, the system pressure was 100kPa, the stirring speed was set to 200r / min, the temperature was gradually increased to 180°C, and then increased to 220°C at a rate of 10°C per hour, and the reaction was continued for 16h to obtain a surface modifier, which was recycled for 20 times and the conversion rate reached 80%. The color of the obtained surface modifier was light yellow.

[0081] Example 5

[0082] A method for preparing a surface modifier comprises the following steps:

[0083] 40g of octadecene, 15.3g of maleic anhydride and 1.90g of hydroquinone supported on alumina were weighed, all added to the reactor and mixed thoroughly, nitrogen was introduced to exhaust the air, the system pressure was 300kPa, the stirring speed was set to 200r / min, the temperature was gradually increased to 180°C, and then increased to 220°C at a rate of 10°C per hour, and the reaction was continued for 16h to obtain a surface modifier, which was recycled for 20 times and the conversion rate reached 85%. The color of the obtained surface modifier was brownish yellow.

[0084] Example 6

[0085] A method for preparing a surface modifier comprises the following steps:

[0086] 40g of n-hexane, 15.3g of oleic acid and 1.90g of hydroquinone were weighed, all added to the reactor and mixed thoroughly, nitrogen was introduced to exhaust the air, the system pressure was 200kPa, the stirring speed was set to 100r / min, the temperature was gradually increased to 180°C, and then increased to 220°C at a rate of 10°C per hour, and the reaction was continued for 16h to obtain a surface modifier, which was recycled for 20 times and the conversion rate reached 78%. The color of the obtained surface modifier was brown-yellow.

[0087] Example 7

[0088] A method for preparing a surface modifier comprises the following steps:

[0089] 40g of n-hexadecane, 15.3g of maleic anhydride and 1.90g of hydroquinone were weighed, all added to the reactor and mixed thoroughly, nitrogen was introduced to exhaust the air, the system pressure was 200kPa, the stirring speed was set to 300r / min, the temperature was gradually increased to 180°C, and then increased to 220°C at a rate of 10°C per hour, and the reaction was continued for 16h to obtain a surface modifier, which was recycled for 20 times and the conversion rate reached 83%. The color of the obtained surface modifier was brownish yellow.

[0090] Example 8

[0091] A method for preparing a surface modifier comprises the following steps:

[0092] 40g of cyclohexane, 15.3g of oleic acid and 1.90g of resorcinol supported on alumina were weighed, all added to the reactor and mixed thoroughly, nitrogen was introduced to exhaust the air, the system pressure was 200kPa, the stirring speed was set to 200r / min, the temperature was gradually increased to 180°C, and then increased to 220°C at a rate of 8°C per hour, and the reaction was continued for 16h to obtain a surface modifier, which was recycled for 20 times and the conversion rate reached 88%. The color of the obtained surface modifier was brownish yellow.

[0093] Example 9

[0094] A method for preparing a surface modifier comprises the following steps:

[0095] 40g of n-hexyne, 15.3g of oleic acid and 1.90g of 2,6-di-tert-butyl-p-cresol supported on silica were weighed, all added to the reactor and mixed thoroughly, nitrogen was introduced to exhaust the air, the system pressure was 200kPa, the stirring speed was set to 200r / min, the temperature was gradually increased to 180°C, and then increased to 220°C at a rate of 12°C per hour, and the reaction was continued for 16h to obtain a surface modifier, which was recycled 20 times and the conversion rate reached 86%. The color of the obtained surface modifier was brown-yellow.

[0096] Example 10

[0097] A method for preparing a surface modifier comprises the following steps:

[0098] 40g of n-eicosane, 15.3g of maleic anhydride and 1.90g of 2,6-di-tert-butyl-p-cresol were weighed, all added to the reactor and mixed thoroughly, nitrogen was introduced to exhaust the air, the system pressure was 200kPa, the stirring speed was set to 200r / min, the temperature was gradually increased to 180°C, and then increased to 210°C at a rate of 10°C per hour, and the reaction was continued for 16h to obtain a surface modifier, which was recycled 20 times and the conversion rate reached 79%. The color of the obtained surface modifier was brown-yellow.

[0099] Embodiment 11

[0100] A method for preparing a surface modifier comprises the following steps:

[0101] 20g of octadecene and 20g of hexadecene, 15.3g of cyclopropane and 1.90g of potassium bromide were weighed, all added to the reactor and mixed thoroughly, nitrogen was introduced to exhaust the air, the system pressure was 200kPa, the stirring speed was set to 200r / min, the temperature was gradually increased to 180°C, and then increased to 230°C at a rate of 10°C per hour, and the reaction was continued for 16h to obtain a surface modifier, which was recycled for 20 times and the conversion rate reached 86%. The color of the obtained surface modifier was brownish yellow.

[0102] Example 12

[0103] A method for preparing a surface modifier comprises the following steps:

[0104] 20g of dodecene and 20g of tetradecene, 15.3g of maleic anhydride and 1.90g of catechol supported on alumina were weighed, all added to the reactor and mixed thoroughly, nitrogen was introduced to exhaust the air, the system pressure was 200kPa, the stirring speed was set to 200r / min, the temperature was gradually increased to 180°C, and then increased to 220°C at a rate of 10°C per hour, and the reaction was continued for 14h to obtain a surface modifier, which was recycled for 20 times and the conversion rate reached 86%. The color of the obtained surface modifier was brownish yellow.

[0105] Example 13

[0106] A method for preparing a surface modifier comprises the following steps:

[0107] 20g of hexadecene and 20g of octadecene, 15.3g of maleic anhydride and 1.90g of catechol were weighed, all added to the reactor and mixed thoroughly, nitrogen was introduced to exhaust the air, the system pressure was 200kPa, the stirring speed was set to 200r / min, the temperature was gradually increased to 180°C, and then increased to 220°C at a rate of 10°C per hour, and the reaction was continued for 14h to obtain a surface modifier, which was recycled for 22 times and the conversion rate reached 88%. The color of the obtained surface modifier was brownish yellow.

[0108] Embodiment 14

[0109] A method for preparing a surface modifier comprises the following steps:

[0110] 20g of tetradecene and 20g of hexadecene, 15.3g of maleic anhydride and 1.90g of catechol supported on titanium dioxide were weighed, all added to the reactor and mixed thoroughly, nitrogen was introduced to exhaust the air, the system pressure was 200kPa, the stirring speed was set to 200r / min, the temperature was gradually increased to 180°C, and then increased to 220°C at a rate of 10°C per hour, and the reaction was continued for 14h to obtain a surface modifier, which was recycled for 25 times and the conversion rate reached 87%. The color of the obtained surface modifier was brownish yellow.

[0111] Embodiment 15

[0112] A method for preparing a surface modifier comprises the following steps:

[0113] 20g of dodecene and 20g of octadecene, 15.3g of maleic anhydride and 1.90g of catechol were weighed, all added to the reactor and mixed thoroughly, nitrogen was introduced to exhaust the air, the system pressure was 200kPa, the stirring speed was set to 200r / min, the temperature was gradually increased to 180°C, and then increased to 220°C at a rate of 10°C per hour, and the reaction was continued for 14h to obtain a surface modifier, which was recycled for 20 times and the conversion rate reached 86%. The color of the obtained surface modifier was brownish yellow.

[0114] Example 16

[0115] A method for preparing a surface modifier comprises the following steps:

[0116] 20g of dodecene and 20g of tetradecene, 15.3g of maleic anhydride and 1.90g of catechol were weighed, all added to the reactor and mixed thoroughly, nitrogen was introduced to exhaust the air, the system pressure was 200kPa, the stirring speed was set to 200r / min, the temperature was gradually increased to 180°C, and then increased to 220°C at a rate of 10°C per hour, and the reaction was continued for 14h to obtain a surface modifier, which was recycled for 22 times and the conversion rate reached 88%. The color of the obtained surface modifier was brownish yellow.

[0117] Embodiment 17

[0118] PVC Mineral Reinforcement Test

[0119] The test method includes the following steps:

[0120] Preparation of samples modified by surface modifier: 60g PVC, 40g calcium carbonate and 0.8g (2wt% of calcium carbonate addition) surface modifier prepared in the above example were treated in a high-speed mixer for 5 minutes to obtain modified samples. The reinforced PVC materials prepared by using the surface modifiers of Examples 1 to 16 are respectively recorded as Sample 1 to Sample 16.

[0121] Preparation of samples not modified by surface modifiers: 60 g of PVC and 40 g of calcium carbonate were processed in a high-speed mixer for 5 min to obtain unmodified samples.

[0122] The above PVC mineral reinforcement test results are shown in Table 1 below.

[0123] Table 1

[0124]

[0125]

[0126] Embodiment 18

[0127] PP High Mineral Filling Test

[0128] The test method includes the following steps:

[0129] Preparation of samples modified with surface modifiers: 70 g PP, 30 g calcium carbonate and 0.8 g (2% of calcium carbonate addition) of the surface modifier prepared in the above example were treated in a high-speed mixer for 5 min to obtain modified samples. The reinforced PP materials prepared with the surface modifiers of Examples 1 to 16 were respectively recorded as Samples 1 to 16.

[0130] Preparation of samples not modified by surface modifiers: 70 g PP and 30 g calcium carbonate were processed in a high-speed mixer for 5 min to obtain unmodified samples.

[0131] The mechanical properties of the samples were tested using the national standard (GB1040-79, plastic tensile test method) to test the tensile properties of the samples. The test results are shown in Table 2 below.

[0132] Table 2

[0133] sample <![CDATA[Impact strength (KJ / M 2 )]]> Tensile properties (MPa) Unmodified ＞130 10.3 Sample 1 ＞130 13.8 Sample 2 ＞130 14.5 Sample 3 ＞130 14.8 Sample 4 ＞130 14.7 Sample 5 ＞130 14.5 Sample 6 ＞130 14.8 Sample 7 ＞130 14.6 Sample 8 ＞130 14.6 Sample 9 ＞130 15.2 Sample 10 ＞130 14.5 Sample 11 ＞130 14.8 Sample 12 ＞130 14.8 Sample 13 ＞130 14.3 Sample 14 ＞130 14.8 Sample 15 ＞130 15.3 Sample 16 ＞130 14.4

[0134] Embodiment 19

[0135] PP general mineral filling test

[0136] The test method includes the following steps:

[0137] Preparation of samples modified by the modifier of the present invention: 60g PP, 40g calcium carbonate and 0.8g (2% of the amount of calcium carbonate added) of the polymer surface modifier prepared in Example 1 above were treated in a high-speed mixer for 5 minutes to obtain a modified sample. The reinforced PVC materials prepared by using the surface modifiers of Examples 1 to 16 above were respectively recorded as Sample 1 to Sample 16.

[0138] Preparation of the sample modified with silane KH560: 60 g PP, 40 g calcium carbonate and 0.8 g (2% of the amount of calcium carbonate added) KH560 were processed in a high-speed mixer for 5 min to obtain the modified sample.

[0139] Preparation of unmodified sample: 60g PP and 40g calcium carbonate were processed in a high-speed mixer for 5min to obtain the unmodified sample.

[0140] After twin-screw compounding, the molded strips were tested and the performance changes after coupling with polymer surface modifier and silane KH560 were compared (silane KH560 is a common coupling agent for calcium powder reinforcement in polypropylene system). The results are shown in Table 3.

[0141] Table 3

[0142] sample <![CDATA[Impact strength (KJ / M 2 )]]> Notch impact (KJ) Tensile properties (MPa) Unmodified ＞130 27 9.15 KH560 modified ＞130 32.5 11.66 Sample 1 ＞130 29 12.24 Sample 2 ＞130 29 13.2 Sample 3 ＞130 29 13.3 Sample 4 ＞130 29 13.5 Sample 5 ＞130 30 13.4 Sample 6 ＞130 29 13.2 Sample 7 ＞130 29 13.2 Sample 8 ＞130 29 13.2 Sample 9 ＞130 29 13.3 Sample 10 ＞130 33 14.2 Sample 11 ＞130 32 13.6 Sample 12 ＞130 29 13.4 Sample 13 ＞130 30 13.5 Sample 14 ＞130 29 13.4 Sample 15 ＞130 29 13.2 Sample 16 ＞130 29 13.2

[0143] Embodiment 20

[0144] PP general mineral reinforcement test

[0145] Preparation of modified samples: 60g PP, 40g calcium carbonate and 0.8g (2% of the amount of calcium carbonate added) of the polymer surface modifier prepared in Example 1 above were treated in a high-speed mixer for 5 minutes to obtain modified samples. The reinforced PVC materials prepared using the surface modifiers of Examples 1 to 16 above were respectively recorded as Sample 1 to Sample 16.

[0146] Preparation of unmodified sample: 60 g PP and 40 g calcium carbonate were processed in a high-speed mixer for 5 min to obtain an unmodified sample.

[0147] The mechanical properties test results of each sample are shown in Table 4.

[0148] Table 4

[0149]

[0150]

[0151] Obviously, the above embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not limitations on the implementation methods of the present invention. For ordinary technicians in the relevant field, other different forms of changes or modifications can be made based on the above description. It is impossible to list all the implementation methods here. All obvious changes or modifications derived from the technical solution of the present invention are still within the protection scope of the present invention.

Claims

1. Application of a surface modifier in polymer modification, characterized in that: The surface modifier is obtained by a semi-Diels-Alder reaction of a compound containing a C=C bond or a C≡C bond with an alkylene oxide, an alkane, an alkene, or maleic anhydride; The olefin is selected from oleic acid, normal olefins or internal olefins; The alkylene oxide is selected from one or more of propylene oxide, butylene oxide and ethylene oxide; The alkane is selected from one or more of n-hexane, n-hexadecane, cyclohexane and n-dodecane; The compound containing a C=C bond is selected from C5-C30 olefins, cis-3-hexenoic acid, oleic acid, and maleic anhydride; The compound containing a C≡C bond is selected from n-hexyne.

2. The use according to claim 1, characterized in that: The internal olefin is selected from one or more of internal-hexene, internal-heptene, internal-octene, internal-nonene, internal-decene, internal-undecene, internal-dodecene, internal-tridecene, internal-tetradecene, internal-pentadecaene, internal-hexadecene, internal-heptadecaene, internal-octadecene, internal-nonadecaene and internal-eicosene.

3. The use according to claim 1, characterized in that: The normal olefin is selected from normal hexene.

4. The use according to claim 1, characterized in that: The molar ratio of the compound containing a C=C bond or a C≡C bond to the alkylene oxide, the alkane, the alkene, and the maleic anhydride is 1:50 to 50:

1.

5. The use according to claim 1, characterized in that: The reaction temperature is 150°C-300°C.

6. The use according to claim 1, characterized in that: The reaction temperature is 200°C-250°C.

7. The use according to claim 1, characterized in that: In the reaction, after the temperature reaches 180°C, it is heated to 200°C-250°C at a rate of 9°C-13°C per hour.

8. The use according to claim 1, characterized in that: The reaction pressure is 100 kPa~1000 kPa.

9. The use according to claim 1, characterized in that: The reaction pressure is 100 kPa to 200 kPa.

10. The use according to claim 1, characterized in that: The reaction time is 5 h to 20 h.

11. The use according to claim 1, characterized in that: The reaction time is 10 h to 20 h.

12. The use according to claim 1, characterized in that: The reaction is carried out under stirring conditions at a stirring rate of 50 to 500 rpm.

13. The use according to claim 1, characterized in that: The reaction is carried out under stirring conditions at a stirring rate of 150 to 300 rpm.

14. The use according to claim 1, characterized in that: The reaction is carried out under anaerobic conditions.

15. The use according to claim 1, characterized in that: The raw materials of the reaction further include an auxiliary agent, and the auxiliary agent includes an effective ingredient, and the effective ingredient includes one or two of 2,6-di-tert-butyl-p-cresol, hydroquinone, potassium halide and methylhydroquinone; The catechol is selected from one of hydroquinone, catechol and resorcinol; The potassium halide is selected from potassium bromide or potassium iodide.

16. The use according to claim 15, characterized in that The auxiliary agent further comprises a carrier, and the active ingredient is loaded on the carrier; The carrier is selected from one or more of alumina, silica and titania.

17. The use according to claim 16, characterized in that The carrier accounts for 0.1%-90% of the total weight of the auxiliary agent.

18. The use according to claim 16, characterized in that The carrier accounts for 0.1%-30% of the total weight of the auxiliary agent.

19. The use according to claim 16, characterized in that: The carrier accounts for 15%-25% of the total weight of the auxiliary agent.

20. The use according to claim 1, characterized in that: The polymer is selected from plastics; The plastic is selected from one or more of polyvinyl chloride and polypropylene.

21. The use according to claim 20, characterized in that The application comprises the following steps: The surface modifier is mixed with a polymer and molded.

22. The use according to claim 21, characterized in that The weight of the surface modifier is 0.1%-5% of the weight of the polymer.

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