CN111087691A

CN111087691A - High-performance high-surface-adhesion polypropylene material suitable for paint spraying and gluing and preparation method thereof

Info

Publication number: CN111087691A
Application number: CN201911337928.8A
Authority: CN
Inventors: 王溢; 张锴; 蔡青; 周文
Original assignee: Shanghai Pret Composites Co Ltd; Zhejiang Pret New Materials Co Ltd; Shanghai Pret Material Technology Co Ltd; Chongqing Pret New Materials Co Ltd; Shanghai Pret Chemical New Materials Co Ltd
Current assignee: Shanghai Pret Composites Co Ltd; Zhejiang Pret New Materials Co Ltd; Shanghai Pret Material Technology Co Ltd; Chongqing Pret New Materials Co Ltd; Shanghai Pret Chemical New Materials Co Ltd
Priority date: 2019-12-23
Filing date: 2019-12-23
Publication date: 2020-05-01

Abstract

The invention discloses a high-performance high-surface-adhesion polypropylene material suitable for spray painting and gluing and a preparation method thereof, wherein the material comprises the following components in percentage by weight: 30.8-89.4% of PP base material; a toughening agent: 0 to 25 percent; 10-40% of a filler; antioxidant: 0.6-2.2%; an adhesion promoter: 0 to 2 percent. The invention has the beneficial effects that: the hyperbranched additive can effectively increase the compatibility between polypropylene and fillers and improve the mechanical property of the material, and the hyperbranched special structure of the additive can obviously increase the melt index of the polypropylene material and improve the processing property of the polypropylene material. Endows the polypropylene material with functional performance, and meets the use requirements of automobile parts such as automobile bumpers, tail gates and the like on the polypropylene material.

Description

High-performance high-surface-adhesion polypropylene material suitable for paint spraying and gluing and preparation method thereof

Technical Field

The invention relates to a polypropylene material endowed with good mechanical property, processability and high surface adhesive force through scientific design of a formula, meets the requirements of parts such as bumpers, tail gates and the like on paint spraying and adhesion experiments of the polypropylene material, is successfully applied to automobile tail gates, and has important significance for realizing light weight of automobiles.

Background

Energy conservation and environmental protection are the subjects of development of the automobile industry in the future, automobile materials are gradually developed towards light weight, functionalization and environmental protection, the occupation ratio of non-metal materials is more than one third of that of common passenger vehicles, and the use of the non-metal materials plays an important role in the aspects of automobile comfort and environmental protection. The non-metallic material has the characteristic of light weight, the increase of the use proportion of the non-metallic material on the automobile is a main way for realizing the lightweight of the automobile, and at present, more and more automobile parts realize the replacement of steel by plastic, wherein the replacement of steel by plastic for the automobile tail door is a hot spot in recent years.

The polypropylene is used as the most widely applied general plastic at present, has the characteristics of light weight, no smell, no toxicity, easiness in processing and the like, is widely applied to interior and exterior trims of automobiles, has the highest occupation ratio in non-metallic materials of automobiles, is widely applied to interior and exterior trim parts such as instrument panels, auxiliary instrument panels, door panels, bumpers and the like at present, is gradually increased in the use of peripheral functional parts of automobile engines such as front end frames, engine covers, intake manifolds and the like, and in recent years, along with the development of new energy automobiles, the use of the polypropylene on tail doors of automobiles becomes a hotspot of research of various main engine plants and modified material plants.

The surface of the automobile part is often sprayed due to special functional requirements, for example, the surface of the part is often sprayed to meet the requirements of appearance and weather resistance, different plastic parts are directly connected together through welding and glue, the special functional requirements of the materials have high surface adhesion, but the polypropylene material has poor polarity due to a molecular structure and is not suitable for surface painting and gluing experiments, even if the surface is subjected to plasma treatment and flame treatment to increase the surface polarity, the procedure is increased to increase the processing cost, the rejection rate is high, and the improvement of the surface adhesion of the polypropylene material through the modification of the material has important significance for the application of the polypropylene material in the automobile part.

Disclosure of Invention

The invention provides a preparation method of a polypropylene material with high performance and high surface adhesion suitable for paint spraying and gluing purposes, and through the design of a formula, a high molecular auxiliary agent with a hyperbranched structure is introduced into the formula, so that the compatibility and the processability of polypropylene and filled minerals are improved, and meanwhile, the polypropylene material is endowed with good surface adhesion, and the preparation method has important significance for the use of the polypropylene material in parts such as bumpers, tail gates and the like.

In order to solve the technical problems, the invention adopts the technical scheme that:

a high-performance high-surface-adhesion polypropylene material suitable for spray painting and adhesive applications comprises the following raw materials in percentage by weight:

the polypropylene raw material can be copolymerized PP or homopolymerized PP, and the melt index of the polypropylene raw material is 10-95 g/10min (230 ℃, 2.16 kg).

The toughening agent is an ethylene-octene copolymer (POE), the POE has good compatibility with PP, and the polypropylene material can be endowed with high impact resistance by adding the toughening agent into the PP.

The filler can be one of talcum powder, wollastonite, glass fiber and the like.

The adhesion promoter C100T is a high molecular weight, non-volatile and environment-friendly auxiliary agent with a hyperbranched structure, and can improve the processability, the sameness with fillers, the surface adhesion and other properties of polypropylene materials.

The composite material can also comprise functional additives such as a lubricant, an antioxidant and the like.

The invention provides a preparation method of a polypropylene material with high performance and surface adhesion suitable for spray painting and gluing, which comprises the following steps:

A. the preparation method of the mineral filled PP material and the chopped glass fiber reinforced PP material comprises the following steps:

(1) weighing polypropylene and various additives according to a formula ratio; uniformly mixing the components by a high-speed stirrer for later use; the fillers are taken according to the formula proportion for standby.

(2) And adding the mixed raw materials through a main feeding port of a double-screw extruder, adding fillers through a side feeding port, and performing melt extrusion, granulation, drying treatment and other processes to obtain the polypropylene material.

B. The preparation method of the long glass fiber reinforced PP material comprises the following steps:

(1) preparing polypropylene modified resin: uniformly mixing polypropylene, a compatilizer or an adhesion promoter and various auxiliaries according to a ratio by using a high-speed stirrer, and adding the mixture into an extruder through a main feeding port of the extruder; the extrusion processing temperature is 140-245 ℃, and the rotating speed of the main machine is 200-450 rpm.

(2) Preparing a long glass fiber reinforced polypropylene material: and (3) impregnating the continuous long glass fiber in the molten polypropylene modified resin melt in an infiltration mold cavity, wherein the impregnation processing temperature is 245-285 ℃, and preparing the long glass fiber reinforced polypropylene material by adopting a pultrusion process.

Compared with the prior art, the invention has the advantages that: by introducing a high molecular weight, non-volatile and environment-friendly auxiliary agent with a hyperbranched structure, the function is as follows: 1. the compatibility of the polypropylene and the filler and the dispersibility of the filler in the polypropylene are improved, so that the mechanical property of the composite material is improved; 2. the fluidity of the material is improved, the dependence on the molten fingers of the base material is reduced, the material is more favorable for the use of thin-wall large parts, and tiger skin lines and the like can be effectively reduced; 3. the additive is added in a small amount, so that the adhesive force can be improved, the success rate of paint spraying and gluing experiments of polypropylene materials is improved, the use requirements of parts such as bumpers and tail doors on the polypropylene materials are met, and compared with the traditional method for increasing the surface adhesive force such as PP-g-MAH, the method has the advantages of small addition amount, obvious effect, no toxicity, no odor and the like.

Detailed Description

In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention clearer, the present invention will be described in further detail with reference to specific embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.

The specific embodiment of the invention selects the following materials:

polypropylene resin A (PP-A): melt index 30, test conditions 230 ℃ 2.16 kg;

polypropylene resin B (PP-B): melt index 50, test conditions 230 ℃ 2.16 kg;

polypropylene resin C (PP-C): melt index 60, test conditions 230 ℃ 2.16 kg;

polypropylene resin D (PP-D): melt index 90, test conditions 230 ℃ 2.16 kg;

talc powder: 3000 mesh, commercially available;

HDPE: 8008, landification;

a toughening agent: POE-6102, Exxon Mobil;

stabilizer-antioxidant 1010: hindered phenolic antioxidants, CIBA, switzerland;

β' -thiodipropionic acid distearate, a stabilizer-antioxidant DSTP, commercially available;

stabilizer-antioxidant 168: phosphite antioxidants, commercially available;

auxiliary agent-7072: henscman chemical engineering;

auxiliary agent-calcium stearate, CaST, lubricant, commercially available;

an adhesion promoter: C100T, wuhan hyperbranched resins, ltd;

black masterbatch 2014, cabot

The product performance testing method comprises the following steps:

melt mass flow index (melt index): the test was carried out according to ISO 1133 at 230 ℃ under a load of 2.16 kg.

Density: according to ISO 1183 method, spline size: 10 x 4 mm.

Tensile property: according to ISO 527 method, spline size: 170 × 10 × 4mm, speed 50 mm/min.

Bending property: according to ISO 178 method, spline size: 80 x 10 x 4mm, speed 2 mm/min.

Notched impact strength: according to ISO 179 method, spline size: 80 x 10 x 4 mm.

Combustion residue: ISO 3451 method.

The rating of adhesion can be judged with reference to the following methods:

A. test method

1, cutting a paint film at a stable pressure and a distance of 1mm (a knife is shown as iron!), and cutting into a grid;

2, lightly sweeping away impurities on the surface, placing the middle of the adhesive tape in parallel with the marking grid, and grinding the adhesive tape by hands;

3 tearing the adhesive tape at an angle close to 60 degrees, keeping the adhesive tape as a reference, and checking the state of the cutting part.

B. Evaluation method

Level 0: the cut edge is completely smooth without any peel-off.

Level 1: there was little coating peeling at the intersection of the cuts, but the cross cut area was not affected significantly more than 5%.

And 2, stage: the coating is stripped at the intersection of the cuts and/or along the edges of the cuts, the affected cross-cut area is significantly greater than 5%, but not significantly greater than 15%.

And 3, level: the cross-cut area affected by partial or total flaking of the coating along the cut edges in large pieces and or in different parts of the grid is significantly greater than 15% but not significantly greater than 35%.

4, level: the coating is stripped along the cutting edge by large fragments and or some squares are partially or completely stripped, and the affected cross cutting area is obviously more than 35 percent but not more than 65 percent.

And 5, stage: the degree of exfoliation was over grade 4.

Example 1:

weighing 2.1kg of PP-B, 4.0kg of PP-C, 1.7kg of POE, 101010 g of antioxidant, DSTP10g of antioxidant and 16820 g of antioxidant; 10g of assistant-calcium stearate, 10g of assistant-707250 g, and adhesion promoters: C100T 100g, black masterbatch 2014100 g; uniformly mixing in a high-speed stirrer to obtain a mixture for later use; weighing 1.8kg of talcum powder for later use

Adding the mixture into a double-screw extruder (the length-diameter ratio of the extruder is 40 and the diameter of the screw is 35mm) through a main feeding port, adding fillers into the extruder through side feeding, controlling the temperature of each section of the double-screw extruder (from the feeding port to a machine head outlet) to be 150 ℃, 210 ℃, 2250 ℃, 225 ℃, 220 ℃, 215 ℃, 210 ℃ and the rotating speed of the double-screw extruder to be 420r/min, cooling extruded strips through a water tank, drying the extruded strips through a blast dryer and then cutting the extruded strips into particles to obtain the product.

The above materials were dried in a forced air drying oven at 100 ℃ for 2h and then injection molded into standard bars at 235 ℃. The injection-molded mechanical property sample strips are tested after being subjected to state adjustment for 24 hours in a standard laboratory environment (23 ℃, 50% RH), and the test results are shown in Table 1.

Example 2:

weighing 2.0kg of PP-A, 4.0kg of PP-C, 1.7kg of POE, 101010 g of antioxidant, DSTP10g of antioxidant and 16820 g of antioxidant; 10g of assistant-calcium stearate, 10g of assistant-707250 g, and adhesion promoters: C100T 200g, black masterbatch 2014100 g; uniformly mixing in a high-speed stirrer to obtain a mixture for later use; weighing 1.8kg of talcum powder for later use

Example 3:

weighing 3.0kg of PP-A, 3.5kg of PP-B, 2.0kg of POE, 101010 g of antioxidant, DSTP10g of antioxidant and 16820 g of antioxidant; 10g of assistant-calcium stearate, 10g of assistant-707250 g, and adhesion promoters: C100T 100g, black masterbatch 2014100 g; uniformly mixing in a high-speed stirrer to obtain a mixture for later use; weighing 1.2kg of talcum powder for later use

Example 4:

weighing 3.0kg of PP-A, 3.4kg of PP-B, 2.0kg of POE, 101010 g of antioxidant, DSTP10g of antioxidant and 16820 g of antioxidant; 10g of assistant-calcium stearate, 10g of assistant-707250 g, and adhesion promoters: C100T 200g, black masterbatch 2014100 g; uniformly mixing in a high-speed stirrer to obtain a mixture for later use; weighing 1.2kg of talcum powder for later use

Example 5:

55kg of polypropylene resin PP-D, 1010100g of antioxidant, 100g of antioxidant DSTP and 168200 g of antioxidant are mixed by using a TE-35 (length-diameter ratio L/D is 48) twin-screw extruder; 100g of assistant-calcium stearate, 100g of assistant-7072500 g, and adhesion promoters: C100T 2kg and black 20141 kg, and the components are uniformly mixed by a high-speed stirrer and then the mixture is added by the main feed of an extruder. The processing temperature is respectively as follows: 140 ℃, 180 ℃, 220 ℃, 230 ℃, 250 ℃, 250 ℃, 265 ℃, 265 ℃ and 380rpm of the main machine.

Preparing a long glass fiber reinforced polypropylene composite material by a pultrusion process of modified polypropylene resin and continuous glass fiber which are subjected to melting reaction by an extruder, wherein the temperature of an impregnation die is 250 ℃, the composite material passes through an impregnation machine head and then is cooled and cut into particles to prepare a long glass fiber reinforced PP particle material with the fiber weight percentage content of 50 percent and the length of the long glass fiber reinforced PP particle material being the same as that of a resin aggregate, preparing a standard mechanical test sample by adopting an injection molding machine, and obtaining a test result shown in Table 1

Comparative example 1:

weighing 2.2kg of PP-B, 4.0kg of PP-C, 1.7kg of POE, 101010 g of antioxidant, DSTP10g of antioxidant and 16820 g of antioxidant; 10g of assistant calcium stearate, 707250 g of assistant and 2014100g of black master batch; uniformly mixing in a high-speed stirrer to obtain a mixture for later use; weighing 1.8kg of talcum powder for later use

Comparative example 2:

weighing 3.0kg of PP-A, 3.6kg of PP-B, 2.0kg of POE, 101010 g of antioxidant, DSTP10g of antioxidant and 16820 g of antioxidant; 10g of assistant calcium stearate, 707250 g of assistant and 2014100g of black master batch; uniformly mixing in a high-speed stirrer to obtain a mixture for later use; weighing 1.2kg of talcum powder for later use

Comparative example 3:

55kg of polypropylene resin PP-D, 1010100g of antioxidant, 100g of antioxidant DSTP and 168200 g of antioxidant are mixed by using a TE-35 (length-diameter ratio L/D is 48) twin-screw extruder; 100g of assistant calcium stearate, 7072500 g of assistant, 5kg of PP-g-MAH and 20141 kg of black master batch are uniformly mixed by a high-speed stirrer, and then the mixture is added by the main feed of an extruder. The processing temperature is respectively as follows: 140 ℃, 180 ℃, 220 ℃, 230 ℃, 250 ℃, 250 ℃, 265 ℃, 265 ℃ and 380rpm of the main machine.

The modified polypropylene resin and the continuous glass fiber which are subjected to melting reaction by the extruder are used for preparing the long glass fiber reinforced polypropylene composite material by a pultrusion process, the temperature of an impregnation die is 250 ℃, the composite material is cooled and cut into granules after passing through an impregnation machine head to prepare the long glass fiber reinforced PP granules with the fiber weight percentage of 50 percent and the length being the same as that of the resin granules, an injection molding machine is used for preparing standard mechanical test samples, and the test results are shown in table 1: and (5) performance test results.

The polypropylene material is light in weight and easy to process, is more applied to the peripheries of automotive interiors, exteriors and engines, and has a functional effect through the design of a material formula, so that the requirements of more parts on the material in the forming and assembling processes are met, and the application of the polypropylene material in automotive functional parts is significant for popularization. The adhesion promoter C100T is an additive with a hyperbranched structure macromolecule, and can endow the material with more functionality when applied to the polypropylene material, through comparing example 1, example 2 and comparative example 1, and example 3, example 4 and comparative example 2, the fluidity and the surface adhesion can be effectively improved by adding the filling polypropylene material C100T, the improvement is remarkable, the mechanical property is also improved, the application of the mineral filling polypropylene material to bumper parts is met, and the improvement of the surface adhesion can effectively improve the success rate of paint spraying. By comparing the example 5 with the comparative example 3, the improvement of the surface adhesion of the C100T is better than that of the PP-g-MAH on the premise of low addition proportion, and the mechanical property is improved to a certain extent, so that the requirements of the all-plastic automobile tail gate on the material are met, and the all-plastic automobile tail gate can be successfully applied to the automobile tail gate project.

Claims

1. A high performance, high surface adhesion polypropylene material suitable for spray paint and adhesive applications, characterized by: the composite material comprises the following raw materials in percentage by weight:

2. the high performance, high surface adhesion polypropylene material for spray paint and adhesive applications of claim 1, wherein: the polypropylene raw material can be copolymerized PP or homopolymerized PP, and the melt index of the polypropylene raw material is 10-95 g/10 min.

3. The high performance, high surface adhesion polypropylene material for spray paint and adhesive applications of claim 1, wherein: the toughening agent is an ethylene-octene copolymer (POE), the POE has good compatibility with PP, and the polypropylene material can be endowed with high impact resistance by adding the toughening agent into the PP.

4. The high performance, high surface adhesion polypropylene material for spray paint and adhesive applications of claim 1, wherein: the filler can be one of talcum powder, wollastonite and glass fiber.

5. The high performance, high surface adhesion polypropylene material for spray paint and adhesive applications of claim 1, wherein: the adhesion promoter C100T is a high molecular weight, non-volatile and environment-friendly assistant with a hyperbranched structure.

6. The high performance, high surface adhesion polypropylene material for spray paint and adhesive applications of claim 1, wherein: and a lubricant and an antioxidant functional auxiliary agent can also be included.

7. A process for the preparation of a high performance, high surface adhesion polypropylene material suitable for spray paint and adhesive applications as claimed in any one of claims 1 to 6, wherein: the method comprises the following steps:

(1) weighing polypropylene and various additives according to a formula ratio; uniformly mixing the components by a high-speed stirrer for later use; taking the filler according to the formula proportion for later use;

(2) adding the mixed raw materials through a main feeding port of a double-screw extruder, adding fillers through a side feeding port, and performing melt extrusion, granulation, drying treatment and other processes to obtain the polypropylene material;

(1) preparing polypropylene modified resin: uniformly mixing polypropylene, a compatilizer or an adhesion promoter and various auxiliaries according to a ratio by using a high-speed stirrer, and adding the mixture into an extruder through a main feeding port of the extruder; the extrusion processing temperature is 140-245 ℃, and the rotating speed of a main machine is 200-450 rpm;