CN110698777A - Modified polypropylene composite material and preparation process thereof - Google Patents
Modified polypropylene composite material and preparation process thereof Download PDFInfo
- Publication number
- CN110698777A CN110698777A CN201910969362.4A CN201910969362A CN110698777A CN 110698777 A CN110698777 A CN 110698777A CN 201910969362 A CN201910969362 A CN 201910969362A CN 110698777 A CN110698777 A CN 110698777A
- Authority
- CN
- China
- Prior art keywords
- rosin
- polypropylene
- parts
- modified polypropylene
- composite material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09F—NATURAL RESINS; FRENCH POLISH; DRYING-OILS; DRIERS (SICCATIVES); TURPENTINE
- C09F1/00—Obtaining purification, or chemical modification of natural resins, e.g. oleo-resins
- C09F1/04—Chemical modification, e.g. esterification
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/322—Ammonium phosphate
- C08K2003/323—Ammonium polyphosphate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Abstract
The invention discloses a modified polypropylene composite material, which comprises the following components in parts by weight: 73-85 parts of colored polypropylene, 12-14 parts of sulfenyl rosin improver, 6-8 parts of fatty alcohol-polyoxyethylene ether ammonium sulfate, 1-2 parts of ammonium polyphosphate and 1-2 parts of nano calcium carbonate. The colored polypropylene prepared by the invention contains a large amount of phenolic hydroxyl, the direct dye grafted on the branched chain contains amino and carboxyl, and the sulfenyl rosin improver contains carboxyl, so that the sulfenyl rosin improver can be combined by a hydrogen bond action in a high-temperature molten state, the sulfenyl rosin improver is loaded on the surface of the colored polypropylene, the rosin has high and low temperature resistance, after silicon-oxygen bonds are introduced into the rosin, the high and low temperature resistance of the rosin is further enhanced due to high bonding energy of the silicon-oxygen bonds, and the rosin is loaded on the surface of the colored polypropylene so as to have a certain protection effect on the colored polypropylene, so that the high and low temperature resistance of the colored polypropylene is improved.
Description
Technical Field
The invention belongs to the field of preparation of polypropylene materials, and relates to a modified polypropylene composite material and a preparation process thereof.
Background
The polypropylene has good chemical stability, can be corroded by concentrated sulfuric acid and concentrated nitric acid, is relatively stable to other various chemical reagents, has good electrical insulating property, and is widely applied to preparation of insulating protective sleeves and the like, but polypropylene products have poor cold resistance and low-temperature impact strength, are easy to age under the action of light, heat and oxygen during use, are poor in coloring property and difficult to color, and the color master batch prepared by directly melting and extruding the polypropylene and a pigment in the existing coloring method is difficult to color, so that the prepared color master batch has uneven color and is easy to fade under the action of ultraviolet rays.
Disclosure of Invention
The invention aims to provide a modified polypropylene composite material and a preparation process thereof, wherein by preparing colored polypropylene, a direct dye can be loaded on the polypropylene through chemical action, so that the load is uniform, the coloring is firm, the color fading is not easy to occur, and the problem of non-uniform color of the existing color master batch is solved.
The purpose of the invention can be realized by the following technical scheme:
the modified polypropylene composite material comprises the following components in parts by weight:
73-85 parts of colored polypropylene, 12-14 parts of sulfenyl rosin improver, 6-8 parts of fatty alcohol-polyoxyethylene ether ammonium sulfate, 1-2 parts of ammonium polyphosphate and 1-2 parts of nano calcium carbonate;
the preparation process of the colored polypropylene comprises the following steps:
step 1: simultaneously adding polypropylene and 4-allyloxy-2-hydroxybenzophenone into an internal mixer, carrying out internal mixing at the temperature of 170-175 ℃ for 1-2min, adding benzoyl peroxide into the mixture, keeping the temperature unchanged, carrying out internal mixing for 50-60min, adding the obtained material into a screw extruder, and carrying out extrusion granulation to obtain modified polypropylene master batch; wherein 0.14-0.16g of 4-allyloxy-2-hydroxybenzophenone and 0.15-0.16g of benzoyl peroxide are added into each gram of polypropylene; the polypropylene generates free radicals under the initiation of benzoyl peroxide, the allyl in the 4-allyloxy-2-hydroxybenzophenone can also generate free radicals under the action of the initiator, so that the polypropylene and the 4-allyloxy-2-hydroxybenzophenone generate free radical reaction, a modified polypropylene master batch prepared by grafting the 4-allyloxy-2-hydroxybenzophenone on a polypropylene side chain contains phenolic hydroxyl, the meta position of the phenolic hydroxyl contains-O-bond, the ortho position contains carbonyl, the phenolic hydroxyl is an adjacent para-position positioning group, the hydrogen on the adjacent para position is compared with the active wave, the carbonyl is a meta-position positioning group, the hydrogen activity of the meta position, namely the para position of the phenolic hydroxyl, is enhanced, the-O-bond is an adjacent para-position positioning group, and the ortho position is the para position of the phenolic hydroxyl, the activity of the para position of the phenolic hydroxyl group is further enhanced through the function of an-O-bond, so that the para position of the phenolic hydroxyl group has extremely high activity and can be reacted;
step 2: dimethyl methyl sulfone, cyclohexanone, ethyl acetate, concentrated sulfuric acid and concentrated nitric acid are mixed according to the mass ratio of 7: 1: 0.3: 1.1: mixing according to the proportion of 0.8 to obtain a mixed solvent, adding the modified polypropylene master batch into the mixed solvent, heating to 120-130 ℃, stirring and dissolving, adding the direct dye into water to prepare a solution with the mass concentration of 55-60%, then adding the direct dye solution and paraformaldehyde into a reaction vessel simultaneously, keeping the temperature unchanged, stirring and reacting for 1-2h, then adding a certain amount of concentrated sulfuric acid into the reaction vessel, keeping the temperature unchanged, performing reflux reaction for 2-3h, then performing evaporation and concentration, and then performing reduced pressure distillation on the concentrated product to obtain colored polypropylene; wherein 11-12mL of mixed solvent is added into each gram of modified polypropylene master batch, 0.18-0.19g of direct dye is added, 0.21-0.22g of paraformaldehyde is added, the volume of concentrated sulfuric acid added for the second time is 7% of the volume of the mixed solvent, as the hydrogen activity of phenolic hydroxyl para-position on the side chain of the modified polypropylene master batch is strong, and the direct pigment contains amino, wherein the amino contains active hydrogen, under the acidic condition, the two can carry out aminomethylation reaction through the paraformaldehyde, so that the direct dye is grafted on the para-position of the phenolic hydroxyl of the side chain of the modified polypropylene master batch, the prepared colored polypropylene directly has the color of the direct dye, and simultaneously, as the direct black dye is uniformly grafted on the side chain of the polypropylene through chemical action, the prepared colored polypropylene has uniform color, and the dyeing effect of the polypropylene is effectively realized, the problems that polypropylene is difficult to color and is not uniform are solved, and meanwhile, because a large number of phenolic hydroxyl groups are uniformly grafted on the polypropylene, hydrogen of the phenolic hydroxyl groups can be dropped to react with free radicals to make the free radicals lose activity, so that the free radical reaction is inhibited;
the sulfur-based rosin improver is prepared by the following specific steps: adding rosin and acetone into a three-neck flask at the same time, stirring and dissolving, then adding benzoyl peroxide into the three-neck flask, heating to 90-95 ℃, stirring and reacting for 30-40min, then respectively dropwise adding thiopropionic acid-S-allyl ester and tetramethyl-tetravinylcyclotetrasiloxane into a reaction container through a dropping funnel, controlling the dropwise adding speed to be 8-9mL/min, controlling the temperature to be unchanged after completely dropwise adding, stirring and reacting for 2-3h, heating to 120-125 ℃, performing reflux reaction for 4-5h, and then evaporating the obtained product to remove the solvent to obtain a sulfur-based rosin modifier; wherein 30-35mL of acetone, 0.9-1g of benzoperoxide, 0.67-0.71g of thiopropionic acid-S-allyl ester and 0.48-0.52g of tetramethyl tetravinylcyclotetrasiloxane are added into each gram of rosin; because the rosin contains unsaturated bonds, the rosin can be subjected to free radical polymerization reaction with S-allyl thiopropionate and tetramethyl tetravinylcyclotetrasiloxane under the initiation of benzoyl peroxide, so that the prepared rosin product contains sulfur and a large amount of silicon;
the specific preparation process of the modified polypropylene composite material comprises the following steps: adding the colored polypropylene and the sulfur-based rosin modifier into an internal mixer at the same time according to a certain proportion, heating to 185 ℃ for plastication for 20-30min, then adding the fatty alcohol-polyoxyethylene ether ammonium sulfate, the ammonium polyphosphate and the nano calcium carbonate into the internal mixer, keeping the temperature unchanged, continuing to plasticate for 60-70s, and then extruding the obtained product through a screw extruder and granulating to obtain the modified polypropylene composite material; because the coloring polypropylene contains a large amount of phenolic hydroxyl, the direct dye grafted on the branched chain contains amino and carboxyl, and the sulfur-based rosin improver contains carboxyl, can be combined through the action of hydrogen bonds in a high-temperature molten state, so that the sulfur-based rosin improver is loaded on the surface of the coloring polypropylene, and because the rosin has higher adhesion effect, the sulfur-based rosin improver can be firmly compounded with the coloring polypropylene, and meanwhile, the rosin has certain softening effect to improve the elasticity of the coloring polypropylene, and the rosin has higher high and low temperature resistance The free radical is inactivated, and then the free radical reaction is inhibited, but hydroperoxide ROOH generated by the reaction is decomposed into new free radicals under a certain concentration, the oxidation reaction of the free radicals is promoted, and sulfur elements contained in an outer rosin layer can convert the ROOH into stable non-free radical compounds, so that the oxidation of a polymer material is completely inhibited, the stabilization effect is achieved, and further the antioxidation effect of the outer rosin layer and the antioxidation effect of an inner coloring polypropylene layer are cooperated, the antioxidation performance of the composite material can be effectively improved, meanwhile, the color fastness and the antioxidation performance of the coloring polypropylene can be improved by the blocking effect of an outer rosin protective layer, and further the coloring polypropylene is effectively prevented from discoloring under the action of high temperature or ultraviolet rays.
The invention has the beneficial effects that:
1. according to the invention, by preparing the colored polypropylene, the direct dye can be loaded on the polypropylene through chemical action, so that the direct dye is uniform in load, firm in coloring and not easy to fade, and the problem of nonuniform color of the existing color master batch is solved.
2. The colored polypropylene prepared by the invention contains a large amount of phenolic hydroxyl and the direct dye grafted on the branched chain contains amino and carboxyl, meanwhile, the sulfur-based rosin improver contains carboxyl, and can be combined through hydrogen bond action in a high-temperature molten state, so that the sulfur-based rosin improver is loaded on the surface of the colored polypropylene, because the rosin has higher adhesive action and can be firmly compounded with the colored polypropylene, and meanwhile, the rosin has a certain softening action and can improve the elasticity of the colored polypropylene, and the rosin has higher high and low temperature resistance, and after silicon-oxygen bonds are introduced into the rosin, the high and low temperature resistance of the rosin is further enhanced due to the high bond energy of the silicon-oxygen bond, and the high and low temperature resistance of the colored polypropylene is improved due to the fact that the rosin is loaded on the surface of the colored polypropylene and further has a certain protection effect on the colored polypropylene.
3. The inner layer of the composite material prepared by the invention is colored polypropylene, the outer layer is a rosin protective layer, hydrogen in phenolic hydroxyl introduced into the polypropylene of the inner layer can fall off to react with free radicals to make the free radicals lose activity so as to inhibit the free radical reaction, but hydroperoxide ROOH generated by the reaction is decomposed into new free radicals at a certain concentration and can promote the oxidation reaction of the free radicals, sulfur element contained in the rosin layer of the outer layer can make the ROOH converted into stable non-free radical compounds so as to completely inhibit the oxidation of polymer materials and play a role in stabilization, so that the antioxidant performance of the composite material can be effectively improved through the synergy of the antioxidant effects of the rosin layer of the outer layer and the colored polypropylene layer of the inner layer, and simultaneously the color fastness and the antioxidant performance of the colored polypropylene can be improved through the blocking effect of the rosin protective layer of the outer layer, thereby effectively preventing the coloring polypropylene from discoloring under the action of high temperature or ultraviolet rays.
Detailed Description
Example 1:
the specific preparation process of the colored polypropylene is as follows:
step 1: simultaneously adding 100g of polypropylene and 14g of 4-allyloxy-2-hydroxybenzophenone into an internal mixer, carrying out internal mixing and mixing at the temperature of 170-175 ℃ for 1-2min, then adding 15g of benzoyl peroxide, keeping the temperature unchanged, carrying out internal mixing for 50-60min, adding the obtained material into a screw extruder, and carrying out extrusion granulation to obtain modified polypropylene master batches;
step 2: dimethyl methyl sulfone, cyclohexanone, ethyl acetate, concentrated sulfuric acid and concentrated nitric acid are mixed according to the mass ratio of 7: 1: 0.3: 1.1: mixing according to the proportion of 0.8 to obtain a mixed solvent, adding 100g of modified polypropylene master batch into 1.1L of the mixed solvent, heating to 120-130 ℃, stirring for dissolving, adding a direct dye into water to prepare a solution with the mass concentration of 55-60%, then simultaneously adding 30g of the direct dye solution and 21g of paraformaldehyde into a reaction vessel, stirring for reaction for 1-2h while keeping the temperature constant, then adding 77mL of concentrated sulfuric acid into the reaction vessel, refluxing for reaction for 2-3h while keeping the temperature constant, then carrying out evaporation concentration, and then carrying out reduced pressure distillation on the concentrated product to obtain the colored polypropylene.
Example 2:
the specific preparation process of the colored polypropylene is as follows: and (3) simultaneously adding 100g of polypropylene and 18g of direct dye into a screw extruder, and carrying out melt extrusion granulation to obtain the colored polypropylene.
Example 3:
the sulfur-based rosin improver is prepared by the following specific steps: adding 100g of rosin and 3L of acetone into a three-neck flask at the same time, stirring and dissolving, then adding 90g of benzoyl peroxide into the three-neck flask, heating to 90-95 ℃, stirring and reacting for 30-40min, then respectively dropwise adding 67g of S-allyl thiopropionate and 48g of tetramethyl-tetravinylcyclotetrasiloxane into a reaction container through a dropping funnel, controlling the dropwise adding speed to be 8-9mL/min, controlling the temperature to be unchanged after the dropwise adding is completed, stirring and reacting for 2-3h, heating to 120-125 ℃, carrying out reflux reaction for 4-5h, and then evaporating the obtained product to remove the solvent therein, thus obtaining the sulfur-based rosin modifier.
Example 4:
the specific preparation of the sulfur-based rosin improver was the same as in example 3, but the preparation was carried out without addition of S-allyl thiopropionate.
Example 5:
the specific preparation of the sulfur-based rosin modifier was the same as in example 3, but the preparation was carried out without the addition of tetramethyltetravinylcyclotetrasiloxane.
Example 6:
the specific preparation process of the modified polypropylene composite material comprises the following steps:
adding 7.3kg of the colored polypropylene prepared in the example 1 and 1.2kg of the sulfur-based rosin improver prepared in the example 3 into an internal mixer at the same time, raising the temperature to 185 ℃ for plastication for 20-30min, then adding 0.6kg of fatty alcohol-polyoxyethylene ether ammonium sulfate, 0.1kg of ammonium polyphosphate and 0.1kg of nano calcium carbonate into the internal mixer, keeping the temperature unchanged, continuing to plasticate for 60-70s, and then extruding the obtained product through a screw extruder and granulating to obtain the modified polypropylene composite material.
Example 7:
the specific procedure for preparing a modified polypropylene composite was the same as in example 6 except that the sulfur-based rosin modifier prepared in example 3 was used instead of the sulfur-based rosin modifier prepared in example 4.
Example 8:
the specific procedure for preparing a modified polypropylene composite was the same as in example 6 except that the sulfur-based rosin modifier prepared in example 3 was used instead of the sulfur-based rosin modifier prepared in example 5.
Example 9:
a modified polypropylene composite was prepared by following the same procedure as in example 6, except that the colored polypropylene prepared in example 1 was used instead of the colored polypropylene prepared in example 2.
Example 10:
the specific preparation process of the modified polypropylene composite material comprises the following steps:
7.3kg of the colored polypropylene prepared in example 2, 210g of S-allyl thiopropionate and 158g of tetramethyltetravinylcyclotetrasiloxane are simultaneously added into an internal mixer to be heated to 185 ℃ for plastication for 20-30min, then 0.6kg of fatty alcohol-polyoxyethylene ether ammonium sulfate, 0.1kg of ammonium polyphosphate and 0.1kg of nano calcium carbonate are added into the internal mixer, the temperature is kept unchanged, plastication is continued for 60-70S, and then the obtained product is extruded by a screw extruder and granulated to obtain the modified polypropylene composite material.
Example 11:
melting the composite materials prepared in examples 6 to 10, adding the melted composite materials into a mold to prepare sheets to be tested, placing the prepared sheets to be tested in a high-temperature box at 90 ℃ and a low-temperature box at-30 ℃ for 6 days, taking out the sheets, and measuring the reduction rate of the tensile strength of the sheets before and after placing the sheets at the high temperature and the low temperature respectively, wherein the reduction rate of the tensile strength is (the tensile strength of the sheets at normal temperature-the tensile strength of the sheets at high/low temperatures)/the tensile strength of the sheets at normal temperature x 100%, and the specific measurement results are shown in table 1;
TABLE 1 determination results of tensile strength change rate of sheet to be measured after standing at high and low temperatures for a certain period of time
| Standing temperature | Example 6 | Example 7 | Example 8 | Example 9 | Example 10 |
| 90℃ | 2.3 | 2.1 | 26.5 | 12.9 | 22.7 |
| -30℃ | 2.1 | 2.2 | 25.8 | 13.1 | 21.6 |
As can be seen from table 1, the tensile strength of the composite materials prepared in examples 6 and 7 does not change much at high and low temperatures, the colored polypropylene contains a large amount of phenolic hydroxyl groups, the direct dye grafted on the branched chain contains amino and carboxyl, and the sulfur-based rosin improver contains carboxyl, so that the sulfur-based rosin improver can be combined by hydrogen bonding in a high-temperature molten state, and the sulfur-based rosin improver is loaded on the surface of the colored polypropylene, and can be firmly combined with the colored polypropylene due to the high adhesive effect of the rosin itself, and the rosin itself has high and low temperature resistance, after the silicon-oxygen bond is introduced into the rosin, the high and low temperature resistance of the rosin is further enhanced due to the high bond energy of the silicon-oxygen bond, and the high and low temperature resistance of the colored polypropylene is improved due to the certain protective effect of the rosin loaded on the surface of the colored polypropylene, the tensile strength of the composite material in the embodiment 8 is greatly reduced, because the high and low temperature resistance of the polypropylene part can be realized through the coating isolation effect of the rosin, but the surface of the rosin has no siloxane, so that the high and low temperature resistance of the polypropylene part is greatly weakened, further the tensile strength of the polypropylene part is weakened, meanwhile, the polypropylene in the embodiment 9 has no grafting reaction, so that the rosin can be coated on the surface of the polypropylene only through the adhesion effect, the coating is not uniform, the protection effect is not uniform, further the tensile strength of the polypropylene part is reduced, meanwhile, in the embodiment 10, the coloring acrylic acid is directly physically mixed with the thiopropionic acid-S-allyl ester and the tetramethyl-tetravinyl cyclotetrasiloxane, although the acrylic acid contains siloxane bonds after mixing, the certain high and low temperature resistance is realized, but the siloxane bonds are easily distributed unevenly due to the physical mixing, and further, the high and low temperature resistance of the resin is uneven, so that the tensile strength of the resin is greatly reduced, and the high and low temperature resistance of the resin is further reduced due to the absence of the coating isolation effect of rosin.
Example 12:
the composite materials prepared in the examples 6 to 10 are melted and added into a mould to prepare a sheet to be tested, and then the sheet is put into a xenon lamp aging test box for aging treatment for 20 days, wherein the ultraviolet illumination intensity is 40mW/cm2The temperature is 50 ℃ and the air humidity is 50%, then the tensile strength of the sample piece before aging is tested, the color of the sample piece is observed, and the measurement result is shown in table 2;
TABLE 2 tensile Strength (MPa) and color Change of the samples after UV aging for a period of time
As shown in Table 2, the color and strength of the test piece in example 6 are not changed much, the direct pigment has unsaturated bonds, and thus the test piece is easy to age and fade under ultraviolet irradiation, so that the gloss is not uniform, while the rosin is loaded on the surface of the colored polypropylene, so that the colored polypropylene has a certain protection effect, the ultraviolet resistance of the colored polypropylene is improved, and the hydrogen in the phenolic hydroxyl group introduced into the polypropylene in the inner layer can be fallen off to react with the free radical, so that the free radical is inactivated, and further the free radical reaction is inhibited, but the generated hydroperoxide ROOH is decomposed into new free radicals at a certain concentration, and the oxidation reaction of the free radicals is promoted, while the sulfur element contained in the outer rosin layer can convert the ROOH into stable non-free radical compounds, so that the oxidation of the polymer material is completely inhibited, and the stabilization effect is achieved, and further the oxidation resistance of the outer rosin layer and the inner colored polypropylene layer is synergistic, the oxidation resistance of the composite material can be effectively improved, and the color fastness and the oxidation resistance of the colored polypropylene can be improved by the blocking effect of the outer rosin protective layer, so that the color of the colored polypropylene of a test piece can be effectively prevented from changing under the action of ultraviolet rays; in example 7, the surface of the colored polypropylene does not contain sulfur, although the colored polypropylene is protected by the rosin layer to be weakened to a certain extent, the inner hydroperoxide ROOH is decomposed into new free radicals at a certain concentration, the oxidation reaction of the free radicals is promoted, the color of the dye is slightly changed, the colored polypropylene does not contain phenolic hydroxyl in example 9, the rosin material is not uniformly dispersed, the coating layer is not uniformly coated, the color brightness and darkness are different, the oxidation resistance of the test piece is reduced due to the absence of phenolic hydroxyl, the ultraviolet protection effect of the test piece is weakened due to the absence of rosin coating in example 10, and the ageing resistance is reduced.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise embodiments disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best utilize the invention. The invention is limited only by the claims and their full scope and equivalents.
Claims (6)
1. The modified polypropylene composite material is characterized by comprising the following components in parts by weight:
73-85 parts of colored polypropylene, 12-14 parts of sulfenyl rosin improver, 6-8 parts of fatty alcohol-polyoxyethylene ether ammonium sulfate, 1-2 parts of ammonium polyphosphate and 1-2 parts of nano calcium carbonate;
the preparation process of the sulfur-based rosin improver comprises the following steps: adding rosin and acetone into a three-neck flask at the same time, stirring and dissolving, then adding benzoyl peroxide into the three-neck flask, heating to 90-95 ℃, stirring and reacting for 30-40min, then respectively dropwise adding thiopropionic acid-S-allyl ester and tetramethyl-tetravinylcyclotetrasiloxane into a reaction container through a dropping funnel, controlling the dropwise adding speed to be 8-9mL/min, controlling the temperature to be unchanged after completely dropwise adding, stirring and reacting for 2-3h, heating to 120-125 ℃, performing reflux reaction for 4-5h, and then evaporating the obtained product to remove the solvent to obtain the sulfur-based rosin modifier.
2. The modified polypropylene composite material of claim 1, wherein the colored polypropylene is prepared by the following steps:
step 1: simultaneously adding polypropylene and 4-allyloxy-2-hydroxybenzophenone into an internal mixer, carrying out internal mixing at the temperature of 170-175 ℃ for 1-2min, adding benzoyl peroxide into the mixture, keeping the temperature unchanged, carrying out internal mixing for 50-60min, adding the obtained material into a screw extruder, and carrying out extrusion granulation to obtain modified polypropylene master batch;
step 2: dimethyl methyl sulfone, cyclohexanone, ethyl acetate, concentrated sulfuric acid and concentrated nitric acid are mixed according to the mass ratio of 7: 1: 0.3: 1.1: 0.8 to obtain a mixed solvent, adding the modified polypropylene master batch into the mixed solvent, heating to 120-130 ℃, stirring and dissolving, adding the direct dye into water to prepare a solution with the mass concentration of 55-60%, then adding the direct dye solution and paraformaldehyde into a reaction vessel simultaneously, keeping the temperature constant, stirring and reacting for 1-2h, then adding a certain amount of concentrated sulfuric acid into the reaction vessel, keeping the temperature constant, performing reflux reaction for 2-3h, then performing evaporation and concentration, and performing reduced pressure distillation on the concentrated product to obtain the colored polypropylene.
3. The modified polypropylene composite material of claim 2, wherein 0.14-0.16g of 4-allyloxy-2-hydroxybenzophenone and 0.15-0.16g of benzoyl peroxide are added per gram of polypropylene in step 1.
4. The modified polypropylene composite material of claim 2, wherein in the step 2, 11-12mL of mixed solvent is added into each gram of modified polypropylene master batch, 0.18-0.19g of direct dye is added, 0.21-0.22g of paraformaldehyde is added, and the volume of concentrated sulfuric acid added for the second time is 7% of the volume of the mixed solvent.
5. The modified polypropylene composite material of claim 1, wherein the rosin is added with 30-35mL of acetone, 0.9-1g of benzamide peroxide, 0.67-0.71g of S-allyl thiopropionate and 0.48-0.52g of tetramethyltetravinylcyclotetrasiloxane per gram of rosin.
6. A preparation process of a modified polypropylene composite material is characterized by comprising the following specific preparation processes: adding the colored polypropylene and the sulfur-based rosin modifier into an internal mixer at the same time according to a certain proportion, raising the temperature to 185 ℃ for plastication for 20-30min, then adding the fatty alcohol-polyoxyethylene ether ammonium sulfate, the ammonium polyphosphate and the nano calcium carbonate into the internal mixer, keeping the temperature unchanged, continuing to plasticate for 60-70s, and then extruding the obtained product through a screw extruder and granulating to obtain the modified polypropylene composite material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910969362.4A CN110698777A (en) | 2019-10-12 | 2019-10-12 | Modified polypropylene composite material and preparation process thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910969362.4A CN110698777A (en) | 2019-10-12 | 2019-10-12 | Modified polypropylene composite material and preparation process thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110698777A true CN110698777A (en) | 2020-01-17 |
Family
ID=69198628
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910969362.4A Pending CN110698777A (en) | 2019-10-12 | 2019-10-12 | Modified polypropylene composite material and preparation process thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110698777A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB931920A (en) * | 1959-12-21 | 1963-07-24 | Eastman Kodak Co | Polypropylene fibres |
| CN87107635A (en) * | 1986-11-05 | 1988-06-01 | 住友化学工业株式会社 | Stainable poly-alpha-olefin composition |
| CN108794885A (en) * | 2018-06-05 | 2018-11-13 | 台州市黄岩广环工贸有限公司 | Anti-aging impact-resistant modified polypropylene material and preparation method thereof |
| CN109575435A (en) * | 2017-09-14 | 2019-04-05 | 株式会社日化精密科技 | The manufacturing method of polypropylene resin composite, acrylic resin formed body and acrylic resin formed body |
-
2019
- 2019-10-12 CN CN201910969362.4A patent/CN110698777A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB931920A (en) * | 1959-12-21 | 1963-07-24 | Eastman Kodak Co | Polypropylene fibres |
| CN87107635A (en) * | 1986-11-05 | 1988-06-01 | 住友化学工业株式会社 | Stainable poly-alpha-olefin composition |
| CN109575435A (en) * | 2017-09-14 | 2019-04-05 | 株式会社日化精密科技 | The manufacturing method of polypropylene resin composite, acrylic resin formed body and acrylic resin formed body |
| CN108794885A (en) * | 2018-06-05 | 2018-11-13 | 台州市黄岩广环工贸有限公司 | Anti-aging impact-resistant modified polypropylene material and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101245169B (en) | Water cooking preventing low-smoke non-halogen flame-proof silicone hydride crosslinked polyolefin composition and method of producing the same | |
| CN110396370B (en) | UV-LED curing modified acrylate pressure-sensitive adhesive and preparation method thereof | |
| CN107177031B (en) | A kind of glycidyl methacrylate modified amine curing agent and resist sagging coating | |
| TWI520938B (en) | Peroxide composition for accelerating crosslink of ethylene-vinylacetate, use therof, and process for production of crosslinked polymer" | |
| CN104327217A (en) | Ultraviolet light cured non-silicon release agent and preparation method thereof | |
| CN108467552A (en) | Light diffusion master batch and preparation method thereof | |
| CN113150448B (en) | Temperature-resistant smooth master batch for solvent-free composite membrane and preparation method thereof | |
| CN110776688B (en) | Antioxidant and anti-UV color master batch and preparation method thereof | |
| CN113402837A (en) | EVA (ethylene-vinyl acetate) treating agent and preparation method thereof | |
| CN110669459B (en) | High-pressure color-changing pressure-sensitive adhesive, preparation method thereof, adhesive tape and application of high-pressure color-changing pressure-sensitive adhesive | |
| KR20110025258A (en) | Adhesive sheet for plating | |
| CN110698777A (en) | Modified polypropylene composite material and preparation process thereof | |
| CN104497405A (en) | Master-batch for EVA coating of solar photovoltaic component, preparation method of master-batch and preparation method of corresponding EVA coating | |
| CN109679007B (en) | High-dispersity quantum dot injection plastic rice and preparation method thereof | |
| CN110300870A (en) | Lampshade | |
| KR100435856B1 (en) | A method for production of a light artificial clay hardening at room temperature | |
| JP5789221B2 (en) | Photosensitive thermoplastic resin composition and molded article using the same | |
| CN113321973B (en) | Treating agent for ultraviolet curing modified EVA/POE material | |
| CN115772372B (en) | Hot melt adhesive composition for aluminum-plastic composite pipe and preparation method thereof | |
| CN116041635A (en) | Antibacterial epoxy ester modified acrylic resin dispersoid and preparation method thereof | |
| CN108752535A (en) | A kind of preparation method of terpene modified photocuring aqueous polyurethane | |
| CN104610897A (en) | Preparation method of acrylic acid modified epoxy resin for LED packaging | |
| CN108530733A (en) | A kind of anti-aging type polyethylene color master batch and preparation method thereof | |
| CN114350281A (en) | Cross-linkable POE composition and application thereof, cross-linked POE film and preparation method and application thereof | |
| CN113512211B (en) | Preparation method of ultraviolet light crosslinked polyolefin master batch |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200117 |