CN104877231A

CN104877231A - Low-temperature impact resistant PP and preparation method thereof

Info

Publication number: CN104877231A
Application number: CN201510133445.1A
Authority: CN
Inventors: 计慷
Original assignee: SUZHOU DELAIER BUILDING MATERIALS SCIENCE AND TECHNOLOGY CO LTD
Current assignee: SUZHOU DELAIER BUILDING MATERIALS SCIENCE AND TECHNOLOGY CO LTD
Priority date: 2015-03-26
Filing date: 2015-03-26
Publication date: 2015-09-02

Abstract

The application discloses low-temperature impact resistant PP and its preparation method. The preparation method comprises the following steps: weighing (by weight) PP, ethylidene norbornene, butadiene, SBS, ethene, SMA, an antioxidant, POE, butylenes, GF, a coupling agent, CPE, nonsaturated siloxane, EPDM and propylene, mixing, extruding, pulling pieces, and granulating. The product is characterized in that flexural modulus is 85-95%; bending strength is 125-145MPa; tensile strength is 30-50MPa, izod impact strength at minus 30 DEG C is 65-85 J/m; heat distortion temperature is 95-115DEG C; Shore hardness is 68-72; and elongation at break is 500-700%.

Description

A kind of low-temperature impact-resistant PP and preparation method thereof

Technical field

The application belongs to PP preparation field, particularly relates to a kind of low-temperature impact-resistant PP and preparation method thereof.

Background technology

Polypropylene is a kind of thermoplastic resin obtained by propylene polymerization.Isotatic polypropylene (isotactic polyprolene), Atactic Polypropelene (atactic polypropylene) and syndiotactic polypropylene (syndiotactic polypropylene) three kinds is divided into by methyl arrangement position.Polypropylene is the polymkeric substance of nontoxic, odorless, tasteless oyster white height crystallization, and density only has 0. 90--, and " 0. 91g/cm3 is one of kind the lightest in current all plastics.It is stable especially to water, and the water-intake rate in water is only 0. 01%, molecular weight about 80,000 one 15 ten thousand.Good moldability, but easily cave in because of large (being 1% ~ 2.5%) thick article of shrinking percentage, to the higher part of some dimensional precisioies, be difficult to reach requirement, product surface good luster, be easy to painted.The polyacrylic industrial production of China starts from 20 century 70s, through the development of more than 30 years, generally define the multiple production technique such as solvent method, liquid-phase bulk-vapor phase process, batch liquid bulk polymerization, vapor phase process to develop simultaneously, the production pattern that large, medium and small industrial scale coexists.The large-scale polypropylene production apparatus of present China is to introduce technology, and medium-sized and small-sized polypropylene production apparatus is based on domestic technology.China's polypropylene output in several years in the future has larger growth, but production still needs for not enough, and China has become global maximum polypropylene net importer.But because output in domestic increases very soon, importation dependence is on a declining curve generally.In China polypropylene coming years, Apparent con-sumption still can keep higher speedup, and import volume will increase, polypropylene industry having a extensive future in China.Be polymerized under acetic acid exists by vinyl acetate between to for plastic, the polymerization degree is advisable with 250 ~ 600, after being polymerized, trace catalyst (being generally superoxide), monomer and (or) solvent remaining in resin are through vacuum-drying, steam stripped, washing or the removing of combination treatment method.Under the existence of acetic acid, take benzoyl peroxide as initiator, vinyl acetate between to for plastic carries out mass polymerization; Or be dispersion agent with polyvinyl alcohol, at 70 ~ 90 DEG C, carry out solution polymerization 2 ~ 6h (polymerization degree controls to be advisable 250 ~ 600) in a solvent, obtain product.

The same side that methyl is arranged in molecular backbone chain claims isotatic polypropylene, if the chaotic both sides being arranged in molecular backbone chain of methyl claim Atactic Polypropelene, the both sides being arranged alternately in molecular backbone chain when methyl claim syndiotactic polypropylene.In the acrylic resin that general industry is produced, isotactic structural content is about 95%, and all the other are random or syndiotactic polypropylene.Industrial products with isotactic thing for main component.Polypropylene also comprises the multipolymer of propylene and a small amount of ethene.Be generally translucent colorless solid, odorless is nontoxic.The highly crystallized due to compound with regular structure, therefore fusing point can up to 167 DEG C.Heat-resisting, corrosion-resistant, the sterilization of goods used vapour is its outstanding advantages.Density is little, is the lightest general-purpose plastics.Shortcoming is that low-temperature impact resistance is poor, more aging, but can be overcome respectively by modification.The PP material of copolymer type has lower heat-drawn wire (100 DEG C), low transparency, low-luster, low rigidity, but has stronger resistance to impact shock, and the shock strength of PP increases along with the increase of ethylene content.The vicat softening temperature of PP is 150 DEG C.Because degree of crystallinity is higher, surface rigidity and the anti-scratch characteristic of this material are fine.There is not environmental stress cracking problem in PP.The melt mass flow rate (MFR) of PP is usually 1 ~ 100.The PP material impact property of low MFR is better but ductility/strength is lower.For the material of identical MFR, the shock strength of copoly type is than the height of homopolymerization type.Due to crystallization, the shrinking percentage of PP is quite high, is generally 1.6 ~ 2.0%.China's household electrical appliance industry development is in recent years rapid, and wide in variety, output is large.Within 2003, China's refrigerator output is 1,850 ten thousand, conditioner forty-two million platform, washing machine 1,700 ten thousand, microwave oven 3,500 ten thousand.According to " 2004 ~ 2006 years Chinese city home theater market survey consultation reports " display, estimate that following 3 Nian Nei China household audio and video system market scales will reach 6,900,000.In addition, various small household appliances also have huge potential market, and this is concerning MODIFIED PP, are fabulous business opportunities.At present, some plastic raw materials manufacturers of China have developed washing machine PP Pipe Compound as PP 1947 is serial, K7726 is serial, receive the welcome of washing machine manufacturer.Therefore, in the coming years, planted agent adds the dynamics of great development household electrical appliance PP PP Pipe Compound, with the demand of adaptation to market variations.

Polyacrylic degree of crystallinity is high, compound with regular structure, thus has excellent mechanical property.The absolute value of Mechanical Properties of PP higher than polyethylene, but still belongs to kind on the low side in a plastic material, and its tensile strength only can reach 30 MPa or slightly high level.The polypropylene that isotactic index is larger has higher tensile strength, but with the raising of isotactic index, the shock strength of material declines to some extent, but no longer changes after dropping to a certain numerical value.Temperature and loading rate very large to polyacrylic Toughness.When temperature is higher than second-order transition temperature, impact fracture is ductile rupture, be brittle rupture, and impact value significantly declines lower than second-order transition temperature.Improve loading rate, the temperature that ductile rupture can be made to change to brittle rupture rises.Polypropylene has excellent flexural fatigue resistance, its goods bent 106 times and do not damage at normal temperatures.But under room temperature and low temperature, because the molecular structure regularity of itself is high, so resistance to impact shock is poor.The most outstanding performance of polypropylene is exactly flexural fatigue resistance, is commonly called as polypropylene (PP).Polypropylene has good thermotolerance, and goods temperature to carry out disinfection sterilizing more than 100 DEG C, and not by under the condition of external force, 150 DEG C also indeformable.Embrittlement temperature is-35 DEG C, embrittlement can occur lower than-35 DEG C, and winter hardiness is not as polyethylene.Reported values for polypropylene glass temperature has a 18qC, 0qC, and 5 DEG C etc., this is also adopt various sample due to people, and wherein contained crystalline phase is different from the ratio of amorphous phase, to make in molecular chain caused by pars amorpha chain length difference.Polyacrylic melt temperature about improves 40 one 50% than polyethylene, and be about 164 1 170 DEG C, 100% grade polypropylene fusing point is 176 DEG C.Polyacrylic chemical stability is fine, outside decapacitation is corroded by the vitriol oil, concentrated nitric acid, all more stable to other various chemical reagent, but low-molecular-weight aliphatic hydrocarbon, aromatic hydrocarbon and chlorinated hydrocarbon etc. can make polypropylene softening and swelling, simultaneously its chemical stability also increases with the increase of degree of crystallinity, so polypropylene is applicable to making various chemical pipeline and accessory, anticorrosion ability is good.It has higher dielectric coefficient, and with the rising of temperature, can be used for making the electrical apparatus insulation goods be heated.Its voltage breakdown is also very high, is suitable as electrical accessorie etc.Reactance voltage, arc resistance are good, but electrostatic degree is high, contact easily aging with copper.Polypropylene is very sensitive to ultraviolet, adds zinc oxide, Tyox B, carbon black or similar milky white filler etc. and can improve its ageing-resistant performance.

Nontoxic, tasteless, density is little, and intensity, rigidity, hardness thermotolerance are all better than low pressure polyethylene, can about 100 DEG C uses.There is good electrical property and high-frequency insulation and not by humidity effect, but become fragile during low temperature, not wear-resisting, easily aging.Be suitable for making common mechanical part, corrosion-resistant part and insulating part.The organic solvents such as common acid, alkali work hardly to it, can be used for tableware.Within 2003, national plastic pipe ultimate production breaks through 1,800,000 t, increases by 23% on a year-on-year basis.In early days, PP tubing is mainly used as agricultural hydraulic pipe, but also there are some problems (resistance to impact shock, ageing-resistant performance are poor) due to early production performance, and market fails to open.Along with first Importing Foreign Advanced Technology of Shanghai Plastic Building Materials Factory, after adopting the tubing of the conveying hot water or cold water of import PP-R material production to obtain market accreditation, existing many producers build PP-R pipe production line at present, price is also constantly fallen after rise by 20,000 ~ 30,000 yuan/t at the initial stage of operation, but the occupation rate of PP-R pipe on plastic pipe market is still very low.According to reflection, current domestic PP-R material compares certain gap in addition with import material, quality haves much room for improvement and improves.It is reported, current Korea S develops a kind of high pressure resistant water service pipe atactic copolymerized polypropene PP-R 112 new grades, and the tubing using this trade mark to produce can use 50 years under 20 DEG C of ultra-high voltage states with 11.2MPa.Plastic pipe is one of major products of applying of China's chemical building material, the Ministry of Construction once sent " about reinforcement Co-polypropylene (PP-R, PP-B) tubing production management and the notice applying work " in calendar year 2001, require that relevant department carries out from raw material, processing, quality jointly so that work such as tubing use, installations, strictly to hold PP pipe workpiece quality to close, in order to carrying out the production of China PP tubing, application, popularization better.Along with people's living standard improves constantly, must bring the requirement and raising that change in all respects differences such as culture, amusement, food, medical treatment, material, indoor decorations, in market, a lot of article use transparent material more and more.Therefore, exploitation transparent PP PP Pipe Compound is a good development trend, and especially need high, the good fluidity of the transparency, shaping fast PP PP Pipe Compound, so that the PP goods that Design and Machining becomes people to like.Transparent PP has more characteristic than common PP, PVC, PET, PS, has more advantages and DEVELOPMENT PROSPECT.In recent years, external transparent PP market growth was very fast, as transparent PP is introduced to the market as PET substitute by Korea S LG; Some company's transparent PP of Germany substitutes PVC; The rate of growth of U.S.'s transparent PP goods exceeds common PP goods 7% ~ 9%; The annual consumption of Japanese PP transparent nucleator is in recent years about 2000t, if calculate with addition 0.25%, the annual production of Japanese transparent PP material can reach 800,000 more than t.According to the introduction of Japan Chemical Co., Ltd., the consumption that Japanese transparent PP PP Pipe Compound is used for microwave cookware and furniture two aspect is maximum.Estimate, within 2005, foreign market is about 5,000,000 ~ 5,500,000 t to transparent PP PP Pipe Compound demand.Current domestic transparent PP PP Pipe Compound and external gap are comparatively large, and production, the application of transparent PP resin and goods thereof still have to be strengthened.And universal along with humanity concept, and the formation of novel harmonious society, designs a kind of low temperature resistant, tensile strength and the high and low-temperature impact-resistant PP that shock strength is high and preparation method thereof of modulus in flexure is very important.

Summary of the invention

the technical problem solved:

The application, for above-mentioned technical problem, provides a kind of low-temperature impact-resistant PP and preparation method thereof, solves existing PP not low temperature resistant, the technical problems such as modulus in flexure, tensile strength and shock strength are low.

technical scheme:

A kind of low-temperature impact-resistant PP, the raw materials by weight portion proportioning of described low-temperature impact-resistant PP is as follows: PP100 part; Ethylidene norbornene 5-15 part; Divinyl 5-25 part; SBS15-35 part; Ethene 10-15 part; SMA20-40 part; Oxidation inhibitor 0.1-0.5 part; POE10-20 part; Butylene 10-30 part; GF is 15-35 part; Coupling agent 0.3-0.7 part; CPE is 15-25 part; Unsaturated siloxane 1-10 part; EPDM5-10 part; Propylene is 10-20 part.

As a preferred technical solution of the present invention: the raw materials by weight portion proportioning of described low-temperature impact-resistant PP is as follows: PP100 part; Ethylidene norbornene 8-12 part; Divinyl 10-20 part; SBS20-30 part; Ethene 11-14 part; SMA25-35 part; Oxidation inhibitor 0.2-0.4 part; POE14-16 part; Butylene 15-25 part; GF is 20-30 part; Coupling agent 0.4-0.6 part; CPE is 17-23 part; Unsaturated siloxane 2-8 part; EPDM6-9 part; Propylene is 11-19 part.

As a preferred technical solution of the present invention: the raw materials by weight portion proportioning of described low-temperature impact-resistant PP is as follows: PP100 part; Ethylidene norbornene 10 parts; Divinyl 15 parts; SBS25 part; Ethene 12 parts; SMA30 part; 0.3 part, oxidation inhibitor; POE15 part; Butylene 20 parts; GF is 25 parts; Coupling agent 0.5 part; CPE is 20 parts; Unsaturated siloxane 5 parts; EPDM8 part; Propylene is 15 parts.

As a preferred technical solution of the present invention: described oxidation inhibitor adopts antioxidant 1010 or anti-oxidant DLTP.

As a preferred technical solution of the present invention: described coupling agent adopts silane coupling agent or aluminate coupling agent.

As a preferred technical solution of the present invention: the preparation method of described low-temperature impact-resistant PP, comprises the steps:

The first step: take PP, ethylidene norbornene, divinyl, SBS, ethene, SMA, oxidation inhibitor, POE, butylene, GF, coupling agent, CPE, unsaturated siloxane, EPDM and propylene according to parts by weight proportioning;

Second step: PP, ethylidene norbornene, divinyl, SBS and ethene are dropped in reactor and is heated to 60-80 DEG C, stir 20-40min;

3rd step: add surplus stock, be warming up to 90-100 DEG C, stirs 40-60min;

4th step: mixed material is dropped in twin screw extruder and extrudes, barrel temperature 170 DEG C, 175 DEG C, 180 DEG C, 185 DEG C, 190 DEG C, 195 DEG C and 200 DEG C.

beneficial effect:

A kind of low-temperature impact-resistant PP of the present invention and preparation method thereof adopts above technical scheme compared with prior art, has following technique effect: 1, product modulus in flexure 1.5-1.6GPa, flexural strength 125-145MPa; 2, tensile strength 30-50MPa ,-30 DEG C of cantilever beam impact strength 65-85 J/m; 3, heat-drawn wire 95-115 DEG C, shore hardness 68-72; 4, elongation at break 500-700%, the widespread production not division of history into periods can replace current material.

Embodiment

embodiment 1:

PP100 part is taken according to parts by weight proportioning; Ethylidene norbornene 5 parts; Divinyl 5 parts; SBS15 part; Ethene 10 parts; SMA20 part; Anti-oxidant DLTP 0.1 part; POE10 part; Butylene 10 parts; GF is 15 parts; Aluminate coupling agent 0.3 part; CPE is 15 parts; Unsaturated siloxane 1 part; EPDM5 part; Propylene is 10 parts.

PP, ethylidene norbornene, divinyl, SBS and ethene are dropped in reactor and is heated to 60 DEG C, stir 20min, add surplus stock, be warming up to 90 DEG C, stir 40min.

Mixed material is dropped in twin screw extruder and extrudes, barrel temperature 170 DEG C, 175 DEG C, 180 DEG C, 185 DEG C, 190 DEG C, 195 DEG C and 200 DEG C.

Modulus in flexure 1.5GPa, flexural strength 125MPa; Tensile strength 30MPa ,-30 DEG C of cantilever beam impact strength 65 J/m; Heat-drawn wire 95 DEG C, shore hardness 68; Elongation at break 500%.

embodiment 2:

PP100 part is taken according to parts by weight proportioning; Ethylidene norbornene 15 parts; Divinyl 25 parts; SBS35 part; Ethene 15 parts; SMA40 part; Anti-oxidant DLTP 0.5 part; POE20 part; Butylene 30 parts; GF is 35 parts; Aluminate coupling agent 0.7 part; CPE is 25 parts; Unsaturated siloxane 10 parts; EPDM10 part; Propylene is 20 parts.

PP, ethylidene norbornene, divinyl, SBS and ethene are dropped in reactor and is heated to 80 DEG C, stir 40min, add surplus stock, be warming up to 100 DEG C, stir 60min.

Modulus in flexure 1.52GPa, flexural strength 130MPa; Tensile strength 35MPa ,-30 DEG C of cantilever beam impact strength 70 J/m; Heat-drawn wire 100 DEG C, shore hardness 69; Elongation at break 550%.

embodiment 3:

PP100 part is taken according to parts by weight proportioning; Ethylidene norbornene 8 parts; Divinyl 10 parts; SBS20 part; Ethene 11 parts; SMA25 part; Antioxidant 1010 is 0.2 part; POE14 part; Butylene 15 parts; GF is 20 parts; Aluminate coupling agent 0.4 part; CPE is 17 parts; Unsaturated siloxane 2 parts; EPDM6 part; Propylene is 11 parts.

Modulus in flexure 1.55GPa, flexural strength 135MPa; Tensile strength 40MPa ,-30 DEG C of cantilever beam impact strength 75 J/m; Heat-drawn wire 105 DEG C, shore hardness 70; Elongation at break 600%.

embodiment 4:

PP100 part is taken according to parts by weight proportioning; Ethylidene norbornene 12 parts; Divinyl 20 parts; SBS30 part; Ethene 14 parts; SMA35 part; Antioxidant 1010 is 0.4 part; POE16 part; Butylene 25 parts; GF is 30 parts; Silane coupling agent 0.6 part; CPE is 23 parts; Unsaturated siloxane 8 parts; EPDM9 part; Propylene is 19 parts.

PP, ethylidene norbornene, divinyl, SBS and ethene are dropped in reactor and is heated to 75 DEG C, stir 35min, add surplus stock, be warming up to 98 DEG C, stir 55min.

Modulus in flexure 1.56GPa, flexural strength 140MPa; Tensile strength 45MPa ,-30 DEG C of cantilever beam impact strength 80J/m; Heat-drawn wire 110 DEG C, shore hardness 71; Elongation at break 650%.

embodiment 5:

PP100 part is taken according to parts by weight proportioning; Ethylidene norbornene 10 parts; Divinyl 15 parts; SBS25 part; Ethene 12 parts; SMA30 part; Antioxidant 1010 is 0.3 part; POE15 part; Butylene 20 parts; GF is 25 parts; Silane coupling agent 0.5 part; CPE is 20 parts; Unsaturated siloxane 5 parts; EPDM8 part; Propylene is 15 parts.

PP, ethylidene norbornene, divinyl, SBS and ethene are dropped in reactor and is heated to 70 DEG C, stir 30min, add surplus stock, be warming up to 95 DEG C, stir 50min.

Modulus in flexure 1.6GPa, flexural strength 145MPa; Tensile strength 50MPa ,-30 DEG C of cantilever beam impact strength 85 J/m; Heat-drawn wire 115 DEG C, shore hardness 72; Elongation at break 700%.

Composition all components in above embodiment all can business be bought.

Above-described embodiment is just for setting forth content of the present invention, instead of restriction, and any change therefore in the implication suitable with claims of the present invention and scope, all should think to be included in the scope of claims.

Claims

1. a low-temperature impact-resistant PP, is characterized in that the raw materials by weight portion proportioning of described low-temperature impact-resistant PP is as follows: PP100 part; Ethylidene norbornene 5-15 part; Divinyl 5-25 part; SBS15-35 part; Ethene 10-15 part; SMA20-40 part; Oxidation inhibitor 0.1-0.5 part; POE10-20 part; Butylene 10-30 part; GF is 15-35 part; Coupling agent 0.3-0.7 part; CPE is 15-25 part; Unsaturated siloxane 1-10 part; EPDM5-10 part; Propylene is 10-20 part.

2. a kind of low-temperature impact-resistant PP according to claim 1, is characterized in that described low-temperature impact-resistant PP raw materials by weight portion proportioning is as follows: PP100 part; Ethylidene norbornene 8-12 part; Divinyl 10-20 part; SBS20-30 part; Ethene 11-14 part; SMA25-35 part; Oxidation inhibitor 0.2-0.4 part; POE14-16 part; Butylene 15-25 part; GF is 20-30 part; Coupling agent 0.4-0.6 part; CPE is 17-23 part; Unsaturated siloxane 2-8 part; EPDM6-9 part; Propylene is 11-19 part.

3. a kind of low-temperature impact-resistant PP according to claim 1, is characterized in that the raw materials by weight portion proportioning of described low-temperature impact-resistant PP is as follows: PP100 part; Ethylidene norbornene 10 parts; Divinyl 15 parts; SBS25 part; Ethene 12 parts; SMA30 part; 0.3 part, oxidation inhibitor; POE15 part; Butylene 20 parts; GF is 25 parts; Coupling agent 0.5 part; CPE is 20 parts; Unsaturated siloxane 5 parts; EPDM8 part; Propylene is 15 parts.

4. a kind of low-temperature impact-resistant PP according to claim 1, is characterized in that: described oxidation inhibitor adopts antioxidant 1010 or anti-oxidant DLTP.

5. a kind of low-temperature impact-resistant PP according to claim 1, is characterized in that: described coupling agent adopts silane coupling agent or aluminate coupling agent.

6. a preparation method of low-temperature impact-resistant PP described in claim 1, is characterized in that, comprise the steps:

3rd step: add surplus stock, be warming up to 90-100 DEG C, stirs 40-60min;