CN102604247B - High-heat-resistance high-rigidity environmentally-friendly polystyrene resin composition and preparation method thereof - Google Patents
High-heat-resistance high-rigidity environmentally-friendly polystyrene resin composition and preparation method thereof Download PDFInfo
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- CN102604247B CN102604247B CN2012100513357A CN201210051335A CN102604247B CN 102604247 B CN102604247 B CN 102604247B CN 2012100513357 A CN2012100513357 A CN 2012100513357A CN 201210051335 A CN201210051335 A CN 201210051335A CN 102604247 B CN102604247 B CN 102604247B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92514—Pressure
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/9258—Velocity
- B29C2948/9259—Angular velocity
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92885—Screw or gear
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92895—Barrel or housing
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Abstract
The invention discloses a high-heat-resistance high-rigidity environmentally-friendly polystyrene resin composition and a preparation method thereof. The polystyrene resin composition contains the following components in percentage by weight: 59-99 percent of polystyrene resin, 0.5-30 percent of SMA (Styrene-Maleic Anhydride) resin, 0-10 percent of stripping agent master batch and 0.01-1 percent of antioxidant, wherein the stripping agent master batch consists of a matrix and a stripping agent. The preparation method has the advantages of simple production process, reduced production cost and capabilities of effectively improving heat resistance and rigidity of polystyrene resin without reducing mechanical property thereof and meanwhile reducing smell and VOC (Volatile Organic Compound) content of the polystyrene resin; and the prepared polystyrene resin composition can be used in the fields of materials with strict requirements on heat resistance and environmental friendliness in packaging materials, daily articles, household appliances, OA (Office Automation), toys, electronic parts and components and equipment, building materials and automobile materials.
Description
Technical field
The present invention relates to a kind of polystyrene resin composite and preparation method thereof.
Background technology
Polystyrene resin is as one of five large general-purpose plastics, have that formability is good, moderate performance, electrical insulating property, agent of low hygroscopicity, easily dyeing and the advantage such as cheap, be widely used in the industries such as packing, electronics, automobile, household electrical appliances, instrument, daily necessities, toy, building.But, polystyrene resin thermotolerance and rigidity are slightly poor, its heat-drawn wire (HDT) is at 80 ℃ of left and right (ASTM D648, load 1.82MPa), cause polystyrene resin to be restricted in the heat-resisting Application Areas of height, as microwave food packaging field, hot drink packaging field and part electric equipment products structure unit etc.Simultaneously, along with the more and more large-scale change of electric equipment products housing, thin-walled property and light-weighted development trend, require polystyrene resin to have good rigidity and heat-resistant deforming performance.
Due in synthetic, preparation, modification and moulding process, styrenic polymer can contain the part volatile matter, generally there is the small-molecule substance of residual monomer, solvent, additive and degraded generation etc. in its source, above-mentioned volatile matter belongs to VOC, common are: a plurality of kinds such as benzene, toluene, ethylbenzene, dimethylbenzene, vinylbenzene, trieline, zellon, formaldehyde and ketone.Along with public's environment protection health consciousness strengthens, people propose requirements at the higher level to indoor climate and Air quality.Styrenic polymer is as household electrical appliances, OA, more material is used in the fields such as wrapping material, daily necessities, toy, sports equipment, footwear material, cable, instrument, electronic devices and components and equipment, material of construction and automotive material, especially household electrical appliances, OA, toy and vehicle material, require more strict to smell and VOC.
At present, improving polystyrene resin thermotolerance and rigidity main path has: improve its molecular weight during 1. by the synthetic polystyrene resin, but because polystyrene resin generally prepares by radical polymerization, the raising molecular weight need to extend generated time and cause on the one hand the crosslinked mechanical properties decrease that causes of rubber phase, can cause on the other hand production cost to improve; 2. add other heat-resistant engineering plastic to form alloy, as polycarbonate (PC) resin, polyphenylene oxide (PPO) resin and maleimide base polymer etc., add above-mentioned resin to cause on the one hand material flowability reduction, processing temperature to improve, cause on the other hand material cost obviously to improve.
The smell and the VOC content main path that reduce polystyrene resin have: 1. by post-synthesis phase process for devolatilization carry out, but extend the devolatilization time or improve the devolatilization temperature, can cause on the one hand polystyrene resin crosslinked/generation such as the degraded side reaction of etc.ing and affect performance, extend on the other hand the devolatilization time or raising devolatilization temperature can improve production cost again greatly.2. the method that adds steam stripping agent is namely adopted in auxiliary devolatilization, also can obviously reduce smell, residual monomer, solvent and the VOC content of styrenic polymer.Mention that as R. J. Ao Erbu Rec " polymer devolatilization " method that adopts single screw extrusion machine and twin screw extruder to introduce simultaneously steam stripping agent carries out devolatilization.And for example United States Patent (USP) 5380822 and 5350813 has been described the method for removing residual monomer in polymkeric substance, and it comprises water filling or suitable condensable fluid in the melt, then allows ejecta flow through flash tank.although steam stripping agent technique can realize suitability for industrialized production, but when directly joining starting material due to steam stripping agent, a large amount of steam stripping agents can not be immersed in starting material, add on the one hand the screw extrusion press operational difficulty, on the other hand, even if join screw extrusion press, because extruder temperature is higher, steam stripping agent is easy to gasification at spout and overflows, do not have the effect of air lift, therefore need to adopt special injection nozzle with capable of regulating flow quantity and injection discharging functions, need simultaneously to add to pressurize the mixing zone for the distribution that improves steam stripping agent and limit steam stripping agent steam and overflow from the target exhaust section, cause aforesaid method all to exist cost higher, operational difficulty etc.
Summary of the invention
For solving above-mentioned the deficiencies in the prior art, primary and foremost purpose of the present invention is to provide a kind of high thermal resistance, high-rigidity environment-friendly type polystyrene resin composite.
Another object of the present invention is to provide the preparation method of above-mentioned high thermal resistance, high-rigidity environment-friendly type polystyrene resin composite.
The present invention is achieved through the following technical solutions:
A kind of high thermal resistance, high-rigidity environment-friendly type polystyrene resin composite by weight percentage, comprises following component:
Polystyrene resin: 59～99%
SMA resin: 0.5～30%
Steam stripping agent master batch: 0～10%
Oxidation inhibitor: 0.01～1%;
Described steam stripping agent master batch is comprised of matrix and steam stripping agent.
Wherein, described polystyrene resin comprises one or more mixtures in General Purpose Polystyrenre resin (GPPS), high-impact polystyrene resin (HIPS) and styrene-butadiene block copolymer (K glue or K-resin).
Described SMA resin has low maleic anhydride content and high molecular feature, and wherein maleic anhydride content is 2～10%, and weight-average molecular weight Mw is 10～300,000.
Described steam stripping agent master batch is comprised of matrix and steam stripping agent; Described matrix has the vesicular structure of one or more dimensions, and its micropore is hatch frame, and micropore size is 0.1 ~ 100nm; Described steam stripping agent is for depressing boiling point and/or flash-point lower than the liquid substance of 200 ℃ at 25 ℃ of normal temperature and standard atmosphere.
Described steam stripping agent master batch matrix is one or more mixtures in wood powder, vegetable fibre, starch, paper, zeolite, molecular sieve, diatomite, silica gel, medical stone, six ring stones, attapulgite clay, porous alumina, polystyrene foamed, expanded polypropylene, expanded polyester and foamed thermoplastic elastomers; Described steam stripping agent is one or more mixtures in part alcohols, white oil, water, solvent oil, edible oil, rubber filling oil, lubricant base, silicone oil and softening agent.
Described oxidation inhibitor is phenols, phosphorous acid esters, contain one or more mixtures in thioesters class and metal passivator.
The preparation method of above-mentioned high thermal resistance, high-rigidity environment-friendly type polystyrene resin composite comprises the following steps:
The preparation of a, steam stripping agent master batch: with the matrix used environment container that is placed in pressure＜0.1MPa of steam stripping agent master batch, then steam stripping agent is injected the environment container, obtain the steam stripping agent master batch;
B, weigh various raw materials by proportioning;
C, each component was mixed in high-speed mixer 3 ~ 5 minutes;
D, with screw extrusion press with the material that mixes melt extrude, granulation, its processing condition are: the twin screw extruder length-to-diameter ratio is 32～40, each subregion temperature of barrel should remain between 50～350 ℃, screw speed is 100～600 rev/mins, the residence time is 0.5～2 minute, and pressure is 5～50MPa.
Described twin screw extruder is provided with one or more natural venting port or vaccum exhaust outlet.
The present invention compared with prior art has following beneficial effect:
1) the present invention adopts the SMA resin of low maleic anhydride content and high molecular feature, maleic anhydride composition and high molecular guarantee that the type SMA resin has high heat-resisting and high rigidity characteristic, and its polarity and polystyrene resin are more or less the same, better with the polystyrene resin consistency, can when increasing substantially polystyrene resin thermotolerance and rigidity, can obviously not affect mechanical property and the processing characteristics of polystyrene resin;
2) the present invention's steam stripping agent master batch used is processed through negative pressure, master batch preparation technology is simple, due to stable being present in the master batch matrix of energy under the steam stripping agent normal temperature and pressure, add screw extrusion press convenient and easy, steam stripping agent can be overcome and shortcoming in starting material can not be directly joined, and screw rod leading portion steam stripping agent can not overflow too early, the air lift successful, and because the steam stripping agent master batch only need to have the container of negative pressure ability, the steam stripping agent that does not need additionally to acquire the cost costliness when adding fashionable screw extrusion press adds device and the conversion unit of melt so low production cost;
3) the present invention adopts the method for steam stripping agent master batch, prepared polystyrene resin composite oder levels can reach 3 grades according to popular PV3900 odor standards, volatile content is reduced to below 0.2%, the vinylbenzene single residual content can be reduced to below 200ppm, TVOC content is reduced to below 200 μ gC/g, effectively reduces smell and the VOC content of styrenic polymer;
4) the prepared polystyrene resin composite of the present invention can be widely used in Material Field heat-resisting in wrapping material, daily necessities, household electrical appliances, OA, toy, sports equipment, footwear material, cable, instrument, electronic devices and components and equipment, material of construction and automotive material and that environmental requirement is strict;
5) the present invention adopts the steam stripping agent master batch to prepare styrene polymer compositions, is convenient to that various auxiliary agents add and starting material mix, and is particularly useful for the composite modification field, prepares various functional composite materials.
Embodiment
Further illustrate the present invention below by embodiment; following examples are the better embodiment of the present invention; but embodiments of the present invention are not subjected to the restriction of following embodiment; other any do not deviate from change, the modification done under spirit of the present invention and principle, substitutes, combination, simplify; all should be the substitute mode of equivalence, within being included in protection scope of the present invention.
Comparative Examples
Weight percent proportioning by the component shown in table 2 takes various raw materials; Each component was mixed in high-speed mixer 3 ~ 5 minutes; With screw extrusion press with the material that mixes melt extrude, granulation, its processing condition are: screw extrusion press has a natural venting port, the twin screw extruder length-to-diameter ratio is 32～40, each subregion temperature of barrel should remain between 50～350 ℃, screw speed is 100～600 rev/mins, the residence time is 0.5～2 minute, and pressure is 5～50MPa.
Embodiment 1
Press table 1 formula and form preparation steam stripping agent master batch, with the steam stripping agent master batch matrix used be placed in negative pressure (the environment container of pressure＜0.1MPa), steam stripping agent injection subnormal ambient container that then will be quantitative obtains the steam stripping agent master batch;
Weight percent proportioning by the component shown in table 2 takes various raw materials, all the other same Comparative Examples.
Embodiment 2
Press table 1 formula and form preparation steam stripping agent master batch, take various raw materials, all the other same Comparative Examples by the weight percent proportioning of the component shown in table 2.
Embodiment 3
Press table 1 formula and form preparation steam stripping agent master batch, take various raw materials, all the other same Comparative Examples by the weight percent proportioning of the component shown in table 2.
Embodiment 4
Press table 1 formula and form preparation steam stripping agent master batch, take various raw materials, all the other same Comparative Examples by the weight percent proportioning of the component shown in table 2.
Embodiment 5
Press table 1 formula and form preparation steam stripping agent master batch, take various raw materials, all the other same Comparative Examples by the weight percent proportioning of the component shown in table 2.
Embodiment 6
Press table 1 formula and form preparation steam stripping agent master batch, take various raw materials, all the other same Comparative Examples by the weight percent proportioning of the component shown in table 2.
Embodiment 7
Press table 1 formula and form preparation steam stripping agent master batch, take various raw materials, all the other same Comparative Examples by the weight percent proportioning of the component shown in table 3.
Embodiment 8
Press table 1 formula and form preparation steam stripping agent master batch, take various raw materials, all the other same Comparative Examples by the weight percent proportioning of the component shown in table 3.
Embodiment 9
Press table 1 formula and form preparation steam stripping agent master batch, take various raw materials, all the other same Comparative Examples by the weight percent proportioning of the component shown in table 3.
Embodiment 10
Press table 1 formula and form preparation steam stripping agent master batch, take various raw materials, all the other same Comparative Examples by the weight percent proportioning of the component shown in table 3.
Embodiment 11
Press table 1 formula and form preparation steam stripping agent master batch, take various raw materials, all the other same Comparative Examples by the weight percent proportioning of the component shown in table 3.
Embodiment 12
Press table 1 formula and form preparation steam stripping agent master batch, take various raw materials, all the other same Comparative Examples by the weight percent proportioning of the component shown in table 3.
Composition and the content of table 1 steam stripping agent master batch
| The component title | Steam stripping agent master batch 1 | Steam stripping agent master batch 2 | Steam stripping agent master batch 3 |
| Hole-opening foaming SBS elastomerics (%) | 70 | ? | ? |
| Hole-opening foaming polystyrene (%) | ? | 70 | ? |
| Molecular sieve (%) | ? | ? | 70 |
| 5# white oil (%) | 30 | ? | ? |
| Water (%) | ? | 30 | ? |
| Methyl alcohol (%) | ? | ? | 30 |
In table 2 Comparative Examples and embodiment, each forms and content
| The component title | Comparative Examples | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 |
| HIPS resin (%) | 99.5 | 99 | 84.5 | 69.5 | 96.5 | 82 | 67 |
| SMA resin (%) | ? | 0.5 | 15 | 30 | 0.5 | 15 | 30 |
| Steam stripping agent master batch 1 (%) | ? | ? | ? | ? | 2.5 | 2.5 | 2.5 |
| Oxidation inhibitor | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
The composition of each component and content in table 3 embodiment
| The component title | Embodiment 7 | Embodiment 8 | Embodiment 9 | Embodiment 10 | Embodiment 11 | Embodiment 12 |
| HIPS resin (%) | 94 | 79.5 | 64.5 | 89 | 74.5 | 59.5 |
| SMA resin (%) | 0.5 | 15 | 30 | 0.5 | 15 | 30 |
| Steam stripping agent master batch 2 (%) | 5 | 5 | 5 | ? | ? | ? |
| Steam stripping agent master batch 3 (%) | ? | ? | ? | 10 | 10 | 10 |
| Oxidation inhibitor | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
Performance evaluation mode and implementation standard:
HDT tests according to standard A STM D648, and concrete grammar is: the 1.82MPa loading is applied on batten, and batten thickness 6.4mm, with the speed heated oil of 2 ° of C/min, the temperature when mensuration batten sag of chain is 0.254mm.
The socle girder notched Izod impact strength is tested according to standard A STM D256, and thickness of sample is 3.2mm;
Modulus in flexure is tested according to ASTM D790, and rate of bending is 2.0mm/min;
The smell assessment is assessed according to the smell evaluation criteria PV3900 of Volkswagen, and evaluation method and standard are as follows:
1) carry out smell by 3 identifiers and identify, if more than 2 points of data deviation, need 5 identifiers;
2) under the standard test room environmental, sample is put into smell assessment particular container bottle, put into the baking oven of 80 ± 5 ℃ and place 2h, when being cooled to 60 ℃, identify assessment by 5 identifiers, then get arithmetical av, round up and implement mark, wherein container bottle is that the popular odor detection standard P V of company 3900 specifies tasteless vial, disturbs to eliminate extraneous material:
Oder levels N=∑ Ni/5
3) judgement criteria such as following table 4:
Table 4 smell judgement criteria
| Scoring | Evaluation |
| 1 | Odorlessness |
| 2 | Scent of, but non interference smell |
| 3 | Obvious smell is arranged, but the non interference smell |
| 4 | The interference smell is arranged |
| 5 | Strong interference smell is arranged |
| 6 | Insupportable smell is arranged |
Fugitive constituent (comprising water) content test method is with reference to GB/T 2914-1999, and concrete grammar is: weighing bottle with cover is placed 1h in the baking oven of 105 ℃, be put in after taking-up and be cooled to room temperature in moisture eliminator, weighing is accurately to 0.0005g; With quality approximately the sample uniform spreading of 5g in weighing bottle bottom, cover lid, then weighing is accurately to 0.0005g, then be positioned over the baking oven of 105 ℃, take out after 1h, put into drying and think highly of and be cooled to room temperature, weighing is accurately to 0.0005g, reheat 0.5h, same operation, until constant weight, namely double weighing result is more or less the same in 0.0005g, calculate thus volatile content, calculation formula is:
Volatile content (%)=(m
0-m
1) * 100/m
0
Wherein, m
0For heating front sample quality, m
1For heating rear sample quality.
Residuce of Styrene content is according to GB/T 16867-1997 standard test, testing method: in the head space bottle, with sample dissolution or swelling and N, in dinethylformamide, use n-butyl benzene as internal standard substance, airtight head space bottle, be placed on the thermal equilibrium of carrying out certain hour under certain temperature, extract the neat injecting chromatograph of a certain amount of thermal equilibrium, carry out the GC quantitative analysis, the peak area according to vinylbenzene and n-butyl benzene of the residual single amount of vinylbenzene calculates.
The head space condition: 120 ℃, 30min
The GC condition:
Chromatographic column: DB-5ms, 50m * 0.32um * 0.32um
Sample size: 2ml
Injector temperature: 200 ℃
Splitting ratio: 50:1
Gas flow rate: 2ml/min
Heating schedule: 50 ℃ of (hold 3min)-10 ℃/min, 200 ℃ (hold 5min)
Carrier gas: He
The organic compound emissions measurement is measured according to TS-INT-002.Testing method: first sample is broken into the fritter of 10-25mg, then takes 1.200 ± 0.0001g sample and put into the head space bottle, seal this bottle and at 120 ℃ of heating 5h, every kind of sample is parallel makees three head space bottles.Syringe is inserted in bottle, volatile organic matter is transferred in gas chromatograph (GC), test conditions is as follows:
The head space condition:
Temperature: 120 ℃, baking oven, 180 ℃ of 150 ℃ of needle tubings and transfer tubes
Time: needle tubing residence time 0.35min, sampling 0.5min
The GC condition:
Gas-chromatography furnace temperature: heat 3min under 50 ℃, be heated to 200 ℃ with 12 ℃/min speed, then at 200 ℃ of constant temperature 4min;
Injector temperature: 200 ℃;
Splitting ratio: 20:1
Enter the front pressure of chromatographic column: 10 psi.
The data of gas-chromatography record comprise total peak area and the peak area of single material.Its peak height should be at more than three times of baseline level of noise, and its peak area should be greater than 0.5g acetone peak area 10% in the 1L butanol solution.The total carbon volatile quantity is calculated by following formula:
E
G=[(A
a-A
o)/K(G)]×2×0.6204
In formula: E
GTotal carbon burst size in=sample, A
aThe peak area that=sample is total, A
o=blank peak area, the calibration factor of K (G)=acetone calibration sample, the coefficient that 2=is relevant to sample quality, the content of carbon in 0.6204=acetone.
With the primary standard of acetone as the volatilization of mensuration total carbon.Respectively a certain amount of acetone is dissolved in the 1L propyl carbinol, as calibration solution.Then extract 2.4 μ L from these solution and be placed in 12mL head space bottle.Peak area with acetone is mapped to the concentration of calibration solution, obtains a curve with linear relationship.Its slope is calibration factor K[K (G) and is the total carbon volatilization, and K (i) is single material volatilization].The equation of working curve as shown in the formula:
Y＝37.03898X+1.18222
In formula: the Y=peak area; The concentration of X=calibration sample (μ g/g)
The performance test results of Comparative Examples and embodiment 1-12 sees the following form 6.
The performance test results of table 6 example composition
| Embodiment | HDT（℃） | Socle girder notched Izod impact strength (J/m) | Modulus in flexure (MPa) | Oder levels | Volatile content (%) | Vinylbenzene single residual content (μ g/g) | TVOC(μgC/g) |
| Comparative Examples | 79 | 11.6 | 2185 | 6.0 | 0.385 | 672 | 436 |
| Embodiment 1 | 80 | 11.3 | 2196 | 6.0 | 0.371 | 657 | 433 |
| Embodiment 2 | 102 | 10.8 | 2382 | 6.0 | 0.302 | 538 | 416 |
| Embodiment 3 | 114 | 10.1 | 2615 | 6.0 | 0.276 | 455 | 408 |
| Embodiment 4 | 78 | 11.7 | 2122 | 5.5 | 0.397 | 488 | 355 |
| Embodiment 5 | 99 | 11.4 | 2284 | 5.0 | 0.454 | 397 | 340 |
| Embodiment 6 | 112 | 11.0 | 2567 | 5.0 | 0.519 | 304 | 301 |
| Embodiment 7 | 81 | 11.2 | 2183 | 3.5 | 0.189 | 317 | 307 |
| Embodiment 8 | 104 | 10.6 | 2364 | 4.0 | 0.258 | 275 | 268 |
| Embodiment 9 | 115 | 10.2 | 2601 | 4.0 | 0.325 | 251 | 211 |
| Embodiment 10 | 83 | 10.8 | 2234 | 3.0 | 0.112 | 208 | 272 |
| Embodiment 11 | 107 | 10.2 | 2415 | 3.0 | 0.185 | 182 | 228 |
| Embodiment 12 | 118 | 9.5 | 2708 | 3.5 | 0..217 | 163 | 197 |
can see from Comparative Examples and embodiment 1 ~ 12, after adding the SMA resin of low maleic anhydride content and high molecular, the HDT of polystyrene resin can reach nearly 120 ℃, more than modulus in flexure reaches 2500MPa, the steam stripping agent master batch of processing through negative pressure can make the smell of material be low to moderate 3.0 grades from 6.0 level down, in material, volatile content is down to 0.2% left and right (the styrenic water content is in 0.2% left and right, therefore should be mainly moisture through volatile content in material after stripping), vinylbenzene single residual content and TVOC can be reduced to respectively 200 μ g/g and below 200 μ gC/g, prepare high heat-resisting, high rigidity, low smell, the polystyrene resin composite of low VOC content.
Claims (9)
1. polystyrene resin composite is characterized in that: by weight percentage, comprise following component:
Polystyrene resin: 59～99%
SMA resin: 0.5～30%
Steam stripping agent master batch: 0～10%
Oxidation inhibitor: 0.01～1%;
Described steam stripping agent master batch is comprised of matrix and steam stripping agent;
The content of described steam stripping agent master batch is not 0.
2. polystyrene resin composite according to claim 1, it is characterized in that: the maleic anhydride content of described SMA resin is 2～10%, weight-average molecular weight Mw is 10～300,000.
3. polystyrene resin composite according to claim 1, it is characterized in that: described matrix has the vesicular structure of one or more dimensions, and its micropore is hatch frame, and micropore size is 0.1 ~ 100nm; Described steam stripping agent is for depressing boiling point and/or flash-point lower than the liquid substance of 200 ℃ at 25 ℃ of normal temperature and standard atmosphere.
4. polystyrene resin composite according to claim 1 is characterized in that: described matrix is one or more mixtures in wood powder, vegetable fibre, starch, paper, zeolite, molecular sieve, diatomite, silica gel, medical stone, six ring stones, attapulgite clay, porous alumina and foamed thermoplastic elastomers.
5. polystyrene resin composite according to claim 1 is characterized in that: described matrix is one or more mixtures in wood powder, vegetable fibre, starch, paper, zeolite, molecular sieve, diatomite, silica gel, medical stone, six ring stones, attapulgite clay, porous alumina, polystyrene foamed, expanded polypropylene and expanded polyester.
6. polystyrene resin composite according to claim 1, it is characterized in that: described steam stripping agent is one or more mixtures in alcohols, white oil, water, solvent oil, edible oil, rubber filling oil, lubricant base, silicone oil and softening agent.
7. polystyrene resin composite according to claim 1 is characterized in that: described oxidation inhibitor is phenols, phosphorous acid esters, contain one or more mixtures in thioesters class and metal passivator.
8. the preparation method of the described polystyrene resin composite of claim 1 ~ 7 any one is characterized in that comprising the following steps:
The preparation of a, steam stripping agent master batch: with the matrix used environment container that is placed in pressure＜0.1MPa of steam stripping agent master batch, then steam stripping agent is injected the environment container, obtain the steam stripping agent master batch;
B, weigh various raw materials by proportioning;
C, each component was mixed in high-speed mixer 3 ~ 5 minutes;
D, with screw extrusion press with the material that mixes melt extrude, granulation, its processing condition are: the twin screw extruder length-to-diameter ratio is 32～40, each subregion temperature of barrel should remain between 50～350 ℃, screw speed is 100～600 rev/mins, the residence time is 0.5～2 minute, and pressure is 5～50MPa.
9. the preparation method of polystyrene resin composite according to claim 8, it is characterized in that: described twin screw extruder is provided with one or more natural venting port or vaccum exhaust outlet.
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| CN102850765B (en) * | 2012-09-12 | 2014-11-12 | 江苏安格特科技发展有限公司 | Preparation method of low-odor polyphenylene ether/polystyrene alloy |
| CN103254499A (en) * | 2013-03-06 | 2013-08-21 | 苏州旭光聚合物有限公司 | Low-smell vehicle polypropylene composite material and its preparation method |
| CN103265784B (en) * | 2013-05-20 | 2016-12-28 | 合肥科拜耳新材料有限公司 | A kind of oil resistant HIPS inner container of icebox material and preparation method thereof |
| CN104119615A (en) * | 2014-07-23 | 2014-10-29 | 广东聚石化学股份有限公司 | Low-TVOC (Total Volatile Organic Compound) and low-luster polypropylene composite for automotive interior trim and preparation method of low-TVOC and low-luster polypropylene composite |
| CN104761840A (en) * | 2015-03-20 | 2015-07-08 | 左正晓 | High-intensity high wear-resistant material used for automobile |
| CN106046553B (en) * | 2016-07-20 | 2019-01-22 | 江林（贵州）高科发展股份有限公司 | The method for reducing volatile organic content in polymer processing |
| CN106353217A (en) * | 2016-08-12 | 2017-01-25 | 泉州市旭丰粉体原料有限公司 | Odor test method |
| CN108997703B (en) * | 2018-08-07 | 2021-06-11 | 浙江新宁生物材料有限公司 | Thermoplastic elastomer and preparation method thereof |
| CN111117142A (en) * | 2019-12-31 | 2020-05-08 | 广东众和中德精细化工研究开发有限公司 | Transparent, heat-resistant and impact-resistant K resin blending material and preparation method thereof |
| CN114213794B (en) * | 2021-11-30 | 2023-08-29 | 金发科技股份有限公司 | Heat-resistant dimensionally stable styrene-based alloy composition and preparation method thereof |
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