CN112724504A - Polypropylene composite material with long-acting fragrance and preparation method and application thereof - Google Patents
Polypropylene composite material with long-acting fragrance and preparation method and application thereof Download PDFInfo
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- -1 Polypropylene Polymers 0.000 title claims abstract description 61
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 60
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 60
- 239000002131 composite material Substances 0.000 title claims abstract description 37
- 239000003205 fragrance Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 48
- 229920000858 Cyclodextrin Polymers 0.000 claims abstract description 34
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 claims abstract description 31
- 235000011175 beta-cyclodextrine Nutrition 0.000 claims abstract description 31
- 239000001116 FEMA 4028 Substances 0.000 claims abstract description 30
- 229960004853 betadex Drugs 0.000 claims abstract description 30
- 239000011347 resin Substances 0.000 claims abstract description 20
- 229920005989 resin Polymers 0.000 claims abstract description 20
- 239000007788 liquid Substances 0.000 claims abstract description 13
- 229920001971 elastomer Polymers 0.000 claims abstract description 10
- 239000000806 elastomer Substances 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 238000011049 filling Methods 0.000 claims abstract description 3
- 239000000796 flavoring agent Substances 0.000 claims description 23
- 235000019634 flavors Nutrition 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 12
- 239000000945 filler Substances 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 10
- 229920001577 copolymer Polymers 0.000 claims description 5
- 244000269722 Thea sinensis Species 0.000 claims description 4
- 239000011256 inorganic filler Substances 0.000 claims description 3
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 3
- 230000005923 long-lasting effect Effects 0.000 claims description 3
- 235000005979 Citrus limon Nutrition 0.000 claims description 2
- 244000131522 Citrus pyriformis Species 0.000 claims description 2
- 229920002943 EPDM rubber Polymers 0.000 claims description 2
- 235000010254 Jasminum officinale Nutrition 0.000 claims description 2
- 240000005385 Jasminum sambac Species 0.000 claims description 2
- 241000234435 Lilium Species 0.000 claims description 2
- 244000242564 Osmanthus fragrans Species 0.000 claims description 2
- 235000019083 Osmanthus fragrans Nutrition 0.000 claims description 2
- 241000220317 Rosa Species 0.000 claims description 2
- 235000006468 Thea sinensis Nutrition 0.000 claims description 2
- 235000020279 black tea Nutrition 0.000 claims description 2
- 235000009569 green tea Nutrition 0.000 claims description 2
- 239000008368 mint flavor Substances 0.000 claims description 2
- 229920002857 polybutadiene Polymers 0.000 claims description 2
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 abstract description 9
- 230000000694 effects Effects 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 150000003384 small molecules Chemical class 0.000 description 10
- 229920001450 Alpha-Cyclodextrin Polymers 0.000 description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- HFHDHCJBZVLPGP-RWMJIURBSA-N alpha-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO HFHDHCJBZVLPGP-RWMJIURBSA-N 0.000 description 6
- 229940043377 alpha-cyclodextrin Drugs 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 238000001125 extrusion Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000013268 sustained release Methods 0.000 description 3
- 239000012730 sustained-release form Substances 0.000 description 3
- 229920004482 WACKER® Polymers 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 2
- 235000013355 food flavoring agent Nutrition 0.000 description 2
- 239000013538 functional additive Substances 0.000 description 2
- GDSRMADSINPKSL-HSEONFRVSA-N gamma-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO GDSRMADSINPKSL-HSEONFRVSA-N 0.000 description 2
- 229940080345 gamma-cyclodextrin Drugs 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000009965 odorless effect Effects 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920005629 polypropylene homopolymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 description 1
- 239000002453 shampoo Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
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
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
-
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a polypropylene composite material with long-acting fragrance, and a preparation method and application thereof. The polypropylene composite material with long-acting fragrance comprises a first master batch and a second master batch which are mixed, wherein the weight ratio of the first master batch to the second master batch is (90-99) to (10-1); the first master batch comprises the following components in parts by weight: polypropylene resin: 35-90 parts of a solvent; filling: 5-40 parts; elastomer: 5-20 parts of a solvent; the second master batch comprises the following components in parts by weight: polypropylene resin: 60-98 parts; liquid essence: 1-20 parts; beta-cyclodextrin: 1-20 parts. The polypropylene composite material takes the beta-cyclodextrin as the fragrance slow-release agent, so that the fragrance of a part prepared from the composite material has a long fragrance quality guarantee period and the characteristic of long-acting fragrance, the VOC level of the part in a vehicle can be always kept at a relatively low position, the sudden increase of the VOC content caused by accelerated release can not occur, and the requirements of related standards are met.
Description
Technical Field
The invention relates to the technical field of high polymer materials, and particularly relates to a polypropylene composite material with long-acting fragrance, and a preparation method and application thereof.
Background
In recent years, due to the requirements of light weight and energy conservation and emission reduction of automobiles, more and more plastic materials are applied to interior and exterior parts of automobiles. The polypropylene material occupies a larger proportion of the plastic for vehicles due to the advantages of excellent comprehensive performance, wide sources, high quality and low price. Due to the existence of tertiary carbon atoms in a molecular structure, a polypropylene material is easy to decompose to generate micromolecular odor substances under the condition of being heated in the processing process, and the conventional modified polypropylene injection molding part usually has certain odor under the comprehensive influence of the micromolecular odor substances contained in various functional additives, so that the comfort of passengers in a vehicle is negatively influenced. Along with the continuous improvement of health consciousness of people, the air quality problem of the environment in the automobile is more and more paid attention by people.
The traditional method for improving the odor of the polypropylene composite material comprises the following steps: the method has the advantages that the odor adsorbent is added in the formula, the extractant is added in the production process to extract micromolecule odor substances, the odor micromolecule is removed by baking treatment, and the like, but the method can only reduce the odor of the composite material particles, and the injection-molded product still has obvious odor due to the fact that the particle injection molding process is repeated once melting and heating process. In order to solve the problem, part of raw material manufacturers adopt a mode of adding a trace amount of flavoring agent (the components of the flavoring agent are the same as those of daily necessities such as shampoo and perfume, and are nontoxic and harmless) in the processing process of the polypropylene composite material to change the taste of the polypropylene composite material, and a fresh and pleasant atmosphere is created in the space in the vehicle to improve the air environment in the vehicle. However, the method has a certain problem that the essence component itself is not completely dissolved with the polypropylene material, and particularly in the high temperature environment in summer, the essence component is accelerated to migrate to the surface of a product and is rapidly released, so that the final aroma gradually becomes thin until disappears with the passage of time, and the original aroma type effect of improving the aroma is lost. In addition, as the components in the essence are mostly micromolecular substances, the VOC level of the whole part can be influenced in the process of quickly accelerating the release of the fragrance along with the lapse of time, so that the VOC in the automobile is increased, and the health of drivers and passengers is influenced.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a polypropylene composite material with long-acting fragrance.
The invention also aims to provide a preparation method of the polypropylene composite material with long-lasting fragrance.
Another object of the present invention is to provide the use of the polypropylene composite with long lasting fragrance.
The above purpose of the invention is realized by the following technical scheme:
a polypropylene composite material with long-acting fragrance is prepared by mixing a first master batch and a second master batch, wherein the weight ratio of the first master batch to the second master batch is (90-99) to (10-1);
the first master batch comprises the following components in parts by weight:
polypropylene resin: 35-90 parts of a solvent;
filling: 5-40 parts;
elastomer: 5-20 parts of a solvent;
the second master batch comprises the following components in parts by weight:
polypropylene resin: 60-98 parts;
liquid essence: 1-20 parts;
beta-cyclodextrin: 1-20 parts.
The inventor finds that the beta-cyclodextrin serving as the fragrance slow-release agent has a cylindrical hollow structure, can envelop fragrance micromolecules and form a relatively stable structure, the fragrance micromolecules can be gradually and slowly released along with the passage of time to play a role in fragrance slow release, and finally macroscopically shows that the smell of a product made of the polypropylene composite material has a long fragrance quality guarantee period and has the characteristic of long-acting fragrance. And the master batch is firstly formed by the master batch and a small amount of polypropylene resin, so that the composite material has better dispersibility.
The beta-cyclodextrin is a ring which is prepared by extracting starch after the action of microbial enzyme and is formed by combining 7 glucose residues by beta-1, 4-glycosidic bonds, and has a cylindrical hollow structure. Generally, the beta-cyclodextrin is present in a dry content of more than 98%. Preferably, the dry content of the beta-cyclodextrin is more than or equal to 99 percent. At this time, the slow-release effect is better.
Preferably, the beta-cyclodextrin is pre-treated to remove volatiles prior to use. In the beta-cyclodextrin, as a part of a cylindrical hollow structure of the beta-cyclodextrin is possibly occupied by other non-fragrant small molecules (such as water molecules), the coating effect of the beta-cyclodextrin on the fragrant small molecules is weakened, the influence can be reduced by the pretreatment of volatile removal, and the better coating effect is ensured.
The volatile removal pretreatment may be by various means known in the art, most commonly by baking.
Preferably, the baking temperature is 50-150 ℃, and the baking time is 12-48 h.
The polypropylene resin comprises homo polypropylene or co-polypropylene; can be one kind or a mixture of several kinds. Typically, the polypropylene resin has a melt flow rate of 0.1 to 150g/10min at 230 ℃ X2.16 kg test conditions.
Preferably, the filler is a filler commonly used for polypropylene resins, typically an inorganic filler. More preferably, the inorganic filler is one or a mixture of more of talcum powder, calcium carbonate, mica, wollastonite and whisker.
Preferably, the filler has a particle size ranging from 1 to 20 μm. Fillers in this range are more suitable for use in polypropylene compositions for the preparation of automotive upholstery.
Preferably, the elastomer is one or more of ethylene-butene copolymer, ethylene-octene copolymer, polybutadiene rubber, ethylene propylene diene monomer rubber and styrene-ethylene-butadiene-styrene copolymer. Generally, the elastomer has a melt flow rate of 0.1 to 30g/10min at 190 ℃ x 2.16 kg.
The liquid fragrance may be a common liquid fragrance. Preferably, the flavor type of the liquid essence is one or more of green tea flavor, black tea flavor, lily flavor, jasmine flavor, lemon flavor, sweet osmanthus flavor, mint flavor or rose flavor.
The preparation method of the polypropylene composite material comprises the following steps:
s1, preparing a first master batch: mixing polypropylene resin, a filler and an elastomer, and then extruding and granulating to obtain the first master batch;
s2, preparing a second master batch: mixing the liquid essence with beta-cyclodextrin to obtain slow-release essence, co-extruding the polypropylene resin and the slow-release essence, wherein the slow-release essence is fed from a side feeding port to obtain the second master batch;
and S3, homogenizing and mixing the first master batch and the second master batch to obtain the polypropylene composite material.
If necessary, other functional additives can be added into the S1. The further functional auxiliaries may be scratch resistance agents, antioxidants or light stabilizers.
Preferably, S1, preparing the obtained first master batch, and further baking the obtained first master batch. The baking treatment is preferably carried out for 12-48 h at 50-150 ℃. By doing so, the volatile matter content of the first master batch can be further reduced, and the odor possibly existing in the first master batch can be reduced.
S2, co-extruding the slow-release essence and the polypropylene resin, preferably by using a double-screw extruder. The screw combination of the double-screw extruder comprises a melting section, a first conveying section, a shearing section, a second conveying section and an extruding section, and a vacuum is preferably extracted from the first conveying section by a high negative pressure strong vacuum pump to remove micromolecular odor substances in the polypropylene resin.
In the present invention, the temperature conditions for the extrusion in S1. and S2 are preferably: the temperature of the first zone is 80-120 ℃, the temperature of the second zone is 190-210 ℃, the temperature of the third zone is 210-230 ℃, the temperature of the fourth zone is 210-230 ℃, the temperature of the fifth zone is 210-230 ℃, the temperature of the sixth zone is 210-230 ℃, the temperature of the seventh zone is 210-230 ℃, the temperature of the eighth zone is 210-230 ℃ and the temperature of the ninth zone is 210-230 ℃. S1 and S2. the rotating speed of the extruded host is 250-800 r/min.
The polypropylene composite material with long-acting fragrance is applied to the preparation of automotive upholstery.
Compared with the prior art, the invention has the following beneficial effects:
the polypropylene composite material with long-acting fragrance provided by the invention takes the beta-cyclodextrin as the fragrance slow-release agent, so that the fragrance of a workpiece prepared from the composite material has a long fragrance quality guarantee period and has the characteristic of long-acting fragrance, the VOC level of the workpiece in a vehicle can be always kept at a relatively low position, the condition that the VOC content suddenly rises due to accelerated release is avoided, and the polypropylene composite material meets the requirements of related standards.
Detailed Description
The present invention will be described in further detail with reference to specific examples and comparative examples, but the present invention is not limited to the examples.
In the examples, the starting materials not specifically mentioned are all conventional commercial products.
The polypropylene resin used in the comparative examples and examples of the present application was a copolymerized polypropylene having a melt flow rate of 25g/min at 230 ℃ under a test weight of 2.16 kg;
the filler A used was talc powder having a particle size D50 of 5 μm, Haicheng addition chemical Co., Ltd;
the filler B used is calcium carbonate with the particle size D50 of 5 mu m, Guangxi Tian Anthrig Yiyi fine calcium carbonate science and technology Limited;
the elastomer used was a 5g/min ethylene-octene copolymer at 190 ℃ with a test weight of 2.16 kg; the used fragrant liquid is green tea-flavored liquid essence;
beta-cyclodextrin A was used, having a dry content of 99.9%, from Wake, Germany; beta-cyclodextrin B was used, having a dry content of 98%, from Wake, Germany; alpha-cyclodextrin, available from wacker, germany, in a dry content of 99.9%; gamma-cyclodextrin, available from wacker, germany, in a dry content of 99.9%; the beta-cyclodextrins of the other examples and comparative examples, except example 5, were subjected to a baking "pre-devolatilization" treatment at 100 ℃ for 24 hours prior to use.
Examples 1 to 10 and comparative examples 1 to 4
According to the formula of table 1, examples 1 to 10 and comparative examples 1 to 4 were prepared, specifically including the following steps:
the preparation method of the polypropylene composite material comprises the following steps:
s1, preparing a first master batch: mixing polypropylene resin, a filler and an elastomer, and then extruding and granulating in a double-screw extruder to obtain the first master batch; after the first masterbatch was prepared, it was optionally subjected to a baking treatment as described in table 1. When the baking treatment is needed, the baking temperature is 100 ℃, and the baking time is 24 h.
S2, preparing a second master batch: mixing liquid essence and beta-cyclodextrin to obtain slow-release essence, co-extruding polypropylene resin and the slow-release essence, wherein the specific co-extrusion operation is carried out by adopting a double-screw extruder, the polypropylene resin is fed from a main feeding port, the screw combination of the double-screw extruder comprises a melting section, a first conveying section, a shearing section, a second conveying section and an extrusion section, wherein the first conveying section adopts a high negative pressure strong vacuum pump (the vacuum degree is-0.12 MPa) to extract vacuum so as to remove micromolecular odor substances, and the slow-release essence is added from a side feeding port in the second conveying section to obtain second master batches;
s3, homogenizing and mixing the first master batch and the second master batch in a homogenizing device to obtain the polypropylene composite material;
and S4, carrying out injection molding on the polypropylene composite material to obtain a finished piece.
S1, and S2 the temperature conditions of the extrusion are as follows: the temperature of the first zone is 100 ℃, the temperature of the second zone is 200 ℃, the temperature of the third zone is 220 ℃, the temperature of the fourth zone is 220 ℃, the temperature of the fifth zone is 220 ℃, the temperature of the sixth zone is 220 ℃, the temperature of the seventh zone is 220 ℃, the temperature of the eighth zone is 220 ℃, the temperature of the ninth zone is 220 ℃, S1 and S2, and the rotating speed of the extruded host is 500 revolutions per minute. The formulations and articles of the examples and comparative examples were tested for odor and VOC as shown in Table 1, with the amounts of each material in Table 1 being parts by weight. Odor ratings were tested using the popular standard PV3900 method. The VOC test was carried out by the commonly accepted bag-method VOC test in the industry, with a bag size of 10L.
TABLE 1
As can be seen from Table 1, the odor levels of comparative example 1 and comparative example 2, which have no flavor release agent beta-cyclodextrin, remain high-concentration odor for 0-30 days, begin to decline at around 90 days, no appreciable flavor is obtained for about 180 days and 360 days, TVOC also shows the same trend, and it is noted that at 30 days, TVOC exceeds the index of not less than 5000 mug/cm3The requirements indicate that the conventional liquid essence has the process of accelerating the release of essence micromolecules in 0-30 days, but the micromolecules are gradually emitted and exhausted after 90 days, and the smell and VOC are gradually reduced; the general trend that the early stage is too thick and the later stage is too thin is presented, and the method is not suitable for the actual expected use scene.
Comparing example 1 and comparative example 1 with each other, it can be seen that after the flavor release agent beta-cyclodextrin is introduced, both the flavor and the VOC show a relatively stable trend, the flavor is sustained and moderate, and the TVOC also remains relatively stable and meets the relevant standards. Comparing example 1 with examples 2-4, it can be seen that the sustained release effect is better under the conditions of the kind and the proportion of the first master batch component, the kind and the proportion of the second master batch component, and the proportion range of the first master batch and the second master batch, and the odor and the TVOC are all kept at proper levels. Although the proportion of the second master batch in example 4 is less than that in example 1, the second master batch can maintain the odor level of 3.5 grade in 0-360 days, but still has better fragrance slow-release capability.
Example 1 compares with example 5 to know that the initial state of beta-cyclodextrin without "pre-devolatilization" is relatively high in odor because a part of the cylindrical hollow structure is occupied by other non-fragrant small molecules (such as water molecules), so that a part of fragrant small molecules are not wrapped, the fragrance is released at an accelerated speed in the early period (within 0-30 days), then after the part of non-wrapped small molecules is released, the slow release of the fragrant small molecules wrapped by the essence slow-release agent is dominant after 30-90 days, and then the steady state of the slow-release state (grade 3.5 is maintained after 90-360 days) is reached, although the beta-cyclodextrin meets the requirements of relevant standards and moderate odor (generally sold on the market in automobile after the production of parts for 30 days), but has the problem that the odor tends to be reduced before and after comparison, therefore, it is preferable to first subject the β -cyclodextrin to a devolatilization treatment during processing.
Comparing example 1 with example 6, it can be known that for beta-cyclodextrin with a dry content of less than 99%, the fragrance is released to a certain extent in an accelerated manner in the early stage (within 0-30 days), and then when the release of the part of uncoated small molecules is finished, the slow release of the fragrance small molecules wrapped by the fragrance slow-release agent is dominant after 30-90 days, and then the steady state of the slow-release state is reached (180 days and 360 days are kept at 3.5 levels). The phase with reduced dry content can be regarded as a reduction in the active ingredient, and the sustained-release effect is affected to some extent, so β -cyclodextrin having a dry content of 99 or more is preferable.
Comparing example 1 with example 7, it can be seen that the odor release effect is consistent and the VOC release effect is substantially the same for different filler types.
As can be seen from comparative examples 3 and 4, when the fragrance sustained-release agent was replaced with another type of cyclodextrin, a similar effect could not be obtained. The structure of the alpha-cyclodextrin is different from that of the beta-cyclodextrin, the size of the inner cavity of the alpha-cyclodextrin is smaller than that of the beta-cyclodextrin, the alpha-cyclodextrin has a stronger effect of enveloping small molecules, once the alpha-cyclodextrin is adsorbed, the small molecules cannot be released after being adsorbed, and the alpha-cyclodextrin does not have a slow release effect, so that the odor grade is kept in a 3.0-grade odorless state from 0 day to 360 days; compared with beta-cyclodextrin, gamma-cyclodextrin has a larger inner cavity and cannot effectively envelop essence micromolecules, so that the whole smell is released quickly, the fragrance micromolecules are quickly removed, a 3.0-grade odorless state is basically presented after 360 days, and the requirement of slow release of the smell is not met.
Claims (10)
1. The polypropylene composite material with long-acting fragrance is characterized by comprising a first master batch and a second master batch which are mixed, wherein the weight ratio of the first master batch to the second master batch is (90-99) to (10-1);
the first master batch comprises the following components in parts by weight:
polypropylene resin: 35-90 parts of a solvent;
filling: 5-40 parts;
elastomer: 5-20 parts of a solvent;
the second master batch comprises the following components in parts by weight:
polypropylene resin: 60-98 parts;
liquid essence: 1-20 parts;
beta-cyclodextrin: 1-20 parts.
2. The polypropylene composite material according to claim 1, wherein the beta-cyclodextrin has a dry content of 99% or more.
3. The polypropylene composite according to claim 1 or 2, wherein the β -cyclodextrin is pre-treated for volatile removal prior to use.
4. The polypropylene composite of claim 3, wherein the volatile removal pretreatment is baking.
5. The polypropylene composite material according to claim 3, wherein the baking temperature is 50-150 ℃, and the baking time is 12-48 h.
6. The polypropylene composite of claim 1, wherein the filler is an inorganic filler.
7. The polypropylene composite material according to claim 1, wherein the elastomer is one or more of ethylene-butene copolymer, ethylene-octene copolymer, polybutadiene rubber, ethylene-propylene-diene rubber, and styrene-ethylene-butadiene-styrene copolymer.
8. The polypropylene composite material according to claim 1, wherein the flavor type of the liquid essence is one or more of green tea flavor, black tea flavor, lily flavor, jasmine flavor, lemon flavor, sweet osmanthus flavor, mint flavor or rose flavor.
9. A method for preparing the polypropylene composite material as claimed in any one of claims 1 to 8, comprising the steps of:
s1, preparing a first master batch: mixing polypropylene resin, a filler and an elastomer, and then extruding and granulating to obtain the first master batch;
s2, preparing a second master batch: mixing the liquid essence with beta-cyclodextrin to obtain slow-release essence, co-extruding the polypropylene resin and the slow-release essence, wherein the slow-release essence is fed from a side feeding port to obtain the second master batch;
and S3, homogenizing and mixing the first master batch and the second master batch to obtain the polypropylene composite material.
10. Use of a polypropylene composite having a long lasting fragrance according to any one of claims 1 to 8 for the preparation of automotive interior trim parts.
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| CN114561065A (en) * | 2021-12-15 | 2022-05-31 | 金发科技股份有限公司 | Polypropylene composite material with biological inductivity and preparation method and application thereof |
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