Summary of 25 plastic reinforced modification formulas and 20 key points involved There are many com
Time:2024-05-16 08:52:29 / Popularity: / Source:
There are many common plastic modification technologies, mainly reinforcement technologies, including fiber reinforcement, self-reinforcement, and molecular reinforcement; toughening technology; filling modification; blending and plastic alloy technology; flame retardant technology; nanocomposite technology; reaction grafting modification; aging resistance; functional modification, including conductive, antistatic, thermal conductive and luminescent, etc.; thermoplastic elastomer technology.
General purpose thermoplastic reinforced formulations
1. High performance glass fiber reinforced PP
Recipe composition:
Homopolymer PP (F401) | 54% |
GF | 30% |
Coupling agent K-550 | 0.5% |
PP-g-MAH | 5% |
POE-g-MAH | 10% |
Lubricant | 0.5% |
Processing conditions:
(1) Extrusion granulation temperature 180~230℃; screw speed 320r/min
(2) Injection molding temperature 190~210℃
Related performance:
(1) Extrusion granulation temperature 180~230℃; screw speed 320r/min
(2) Injection molding temperature 190~210℃
Related performance:
Tensile strength/MPa | 70 |
Flexural elastic modulus/GPa | 1.5 |
Heat distortion temperature/℃ | 160 |
Impact strength/(J/m2) | 40 |
2. Glass fiber reinforced PP
Recipe composition:
PP | 51% |
LDPE | 5% |
Glass fiber (5mm) | 40% |
Maleated PP | 4% |
Related performance:
Tensile strength/MPa | 97 |
Flexural elastic modulus/GPa | 7.44 |
Impact strength/(J/m2) | 138.8 |
3. Glass fiber reinforced PP
Recipe composition:
PP | 58% |
Silane treated fiberglass | 30% |
Pulp | 6% |
Unsaturated carboxylic acid modified polyolefin | 6% |
4. GF/liquid crystal composite reinforced PP
Recipe composition:
PP | 70% |
TLCP | 5% |
GF | 30% |
Note: GF length is less than 4mm, treated with bismaleimide, TLCP thermotropic solution polymer, copolyester of parahydroxybenzoic acid (PHB) and PET (60/40).
Related performance:
Tensile strength 51.3MPa; tensile modulus 1.59GPa.
Related performance:
Tensile strength 51.3MPa; tensile modulus 1.59GPa.
5. Mica reinforced PP
Formula composition (mass parts):
PP | 100 |
Silane coupling agent | 0.25 |
Mica | 30 |
Related performance:
Tensile strength/MPa | 50 |
Bending strength/MPa | 82 |
Rockwell hardness (R) | 106 |
Heat distortion temperature ℃ | 128 |
Product warpage deformation/% | 1.2 |
6. Chopped glass fiber reinforced PP
Formula composition (mass parts):
PP | 100 |
CaSt | 0.5 |
Activated chopped glass fiber | 30 |
Antioxidant 1010 | 0.3 |
A-174 coupling agent | 0.1 |
Auxiliary antioxidant DLTP | 0.5 |
Related performance:
Tensile strength/MPa | 37.32 |
Elastic modulus/MPa | 252.19 |
Notched impact strength/kJ/m2 | 8.15 |
Unnotched impact strength/kJ/m2 | 29.55 |
Heat distortion temperature/℃ | 124.5 |
7. Wollastonite fiber-filled reinforced PP
PP | 100 |
CaSt | 0.5 |
Wollastonite fiber | 30 |
Antioxidant 1010 | 0.3 |
KH-550 | 0.5~1 |
Auxiliary antioxidant DLTP | 0.3 |
Related performance:
Tensile strength/MPa | 28.54 |
Elastic modulus/MPa | 201.92 |
Notched impact strength/kJ/m2 | 8.32 |
Unnotched impact strength/kJ/m2 | 32.10 |
Heat distortion temperature/℃ | 124.5 |
8. Composite reinforced PP
Formula composition (mass parts):
PP (Yanshan Petrochemical 1300) | 100 |
Mica powder | 15 |
fiberglass | 25 |
Silane coupling agent | 0.5~1 |
Related performance:
Tensile strength/MPa | 86.8 |
Flexural modulus/MPa | 4200 |
Notched impact strength/kJ/m2 | 7.1 |
Unnotched impact strength/kJ/m2 | 20.1 |
Heat distortion temperature/℃ | 124.5 |
9. Glass fiber reinforced PVC
Formula composition (mass parts):
PVC | 100 |
Thiol dibutene | 3 |
Surface coated fiberglass | 30 |
HSt | 0.5 |
Processing conditions: After each component in formula is fully mixed, it is extruded into finished product.
Related performance:
Bending strength/MPa | 113.7 |
Heat distortion temperature/℃ | 80.5 |
Izod impact strength/kJ/m2 | 19.1 |
10. Glass fiber reinforced PVC
Recipe composition:
PVC | 100 |
Fatty acids | 1 |
Dibasic lead sulfate | 3 |
CaSt | 0.3 |
Fatty acid ester | 2 |
Glass fiber (2~4mm) | 30 |
Engineering plastic reinforced formula
1. Long glass fiber reinforced PA6
Recipe composition:
- | 1# | 2# |
PA6 | 67.8 | 63.9 |
PP-g-MA | - | 4 |
Long glass fiber (10mm) | 32.2 | 32.1 |
Related performance:
1 | 1# | 2# |
Tensile strength/MPa | 208.4 | 208.6 |
Bending strength/MPa | 269.5 | 249.0 |
Impact strength/kJ/m2 | 63.4 | 68.7 |
Notched impact strength/kJ/m2 | 29.0 | 32.3 |
2. Flame retardant and antistatic reinforced PA6
Recipe composition:
PA6 | 40~55 |
Flame retardant | 15~25 |
Toughening agent | 5~8 |
Antistatic agent | 5~8 |
Glass fiber | 25~30 |
3. Antistatic glass fiber reinforced PA6 impeller
Recipe composition:
Short glass fiber reinforced PA6 (containing 30% glass fiber) | 94% |
Short carbon fiber | 4.5% |
Conductive carbon black | 0.5% |
4. Flame retardant glass fiber reinforced PA6 impeller
Recipe composition:
Short glass fiber reinforced PA6 (containing 30% glass fiber) | 91% |
Melamine | 4% |
Sb2O3 | 5% |
5. Transparent glass fiber reinforced PC
PC | 100 |
Polyethylene | 13.7 |
Fiberglass cut into bundles | 49 |
Silane coupling agent | 0.33 |
Related performance:
Young's modulus | 6.95GPa |
Flexural modulus | 170MPa |
Turbidity | 28% |
Transmittance | 85% |
Thermoset reinforced formulations
1. Enhanced PF for chemical anti-corrosion pipelines
Recipe composition:
Homopolymer PP (F401) | 100 |
Wet asbestos | 8 |
crocidolite | 152 |
2. Epoxy fiberglass (1)
Epoxy resin (E-44) | 100 |
Ethylenediamine (65%) | 6~8 |
Dibutyl phthalate | 10~15 |
Filling | 30~40 |
Triphenyl phosphite | 5 |
Acetone (or absolute ethanol) | 10~15 |
3. Epoxy fiberglass (2)
Epoxy resin (E-44) | 100 |
Ethylenediamine (65%) | 6~8 |
Dibutyl phthalate | 10~15 |
Filling | 30~40 |
Metaphenylenediamine | 15 |
Acetone (or absolute ethanol) | 20~30 |
4. Epoxy phenolic fiberglass
Recipe composition:
Epoxy resin (E-44) | 80(70) |
Phenolic resin (2130) | 20 (30) |
Polyester resin (304) | 10 |
Dibutyl phthalate | 10 |
Filler (rock powder, graphite powder, quartz powder) | 20~30 |
Metaphenylenediamine | 14~16 |
Acetone (or absolute ethanol) | 10~15 |
5. Epoxy furan fiberglass
Recipe composition:
Epoxy resin (E-44) | 30 |
Furan resin | 70 |
Triphenyl phosphite | 10 |
Dibutyl phthalate | 10 |
Filler (rock powder, graphite powder, quartz powder) | 30 |
Ethylenediamine | 6~8 |
Acetone (or absolute ethanol) | 10~15 |
Processing conditions: Heating and curing, generally 80~90℃×4h
6. No. 771 unsaturated polyester fiberglass
Recipe composition:
No. 771 unsaturated polyester | 100 |
Cobalt naphthenate or cobalt naphthenate | 3~4 in winter, 0.5~1 in summer |
Cyclohexanone peroxide | 1 |
7. High strength unsaturated polyester board
Recipe composition:
Propylene glycol/neopentyl glycol/isophthalic acid/fumaric acid condensation UP | 100 |
Styrene | 43 |
PMMA | 29 |
ZnSt | 4 |
Hydroperoxide tert-butyl | 3 |
1,3-bis(tert-peroxyisopropyl)benzene | 1.5 |
Other plastic reinforced formulations
1. GF enhanced RJM-PU
Recipe composition:
Carbodiimide modified liquefied MDF | 63 |
PAPI | 10 |
End-capped polyether glycol | 100 |
Dibutylene dilaurate | 0.25 |
Butanediol | 20 |
Fiberglass | 30 |
2. Glass fiber reinforced PVDC special-shaped components
Recipe composition:
PVDC | 25 |
VC, VDC | 25 |
Fiberglass | 50 |
Colorant | 12 |
3. UHMWPE/carbon fiber composite materials
Recipe composition:
UHMWPE | 80% |
EVA | 3% |
Carbon fiber | 12% |
Carbon black | 5% |
20 key points in plastic modification
1 Masterbatch core
Amount of masterbatch core in masterbatch is generally more than 20%.
2 Dispersant
Its function is to make filler have good compatibility with carrier resin, melting point and melt viscosity should be lower than carrier resin. Common dispersants include stearic acid and its salts, erucamide, solid paraffin, liquid paraffin, polyethylene wax (ie relative molecular weight polyethylene), oxidized PE, α-methylstyrene, etc.
Dispersant has a low melting point and can melt quickly when temperature rises, coats surface of inorganic filler that has been treated with coupling agent and cross-linking agent, making surface tension of masterbatch closer to that of main resin, thereby greatly improving dispersion of inorganic fillers, reducing viscosity of composite material, and improving fluidity. General dosage is about 5%.
Dispersant has a low melting point and can melt quickly when temperature rises, coats surface of inorganic filler that has been treated with coupling agent and cross-linking agent, making surface tension of masterbatch closer to that of main resin, thereby greatly improving dispersion of inorganic fillers, reducing viscosity of composite material, and improving fluidity. General dosage is about 5%.
3 Carrier resin
The key to whether filling masterbatch can be evenly dispersed in main resin is choice of carrier resin. Atactic polypropylene has a low soft point and has a good coating effect on calcium carbonate and other particles. Melt flow rate of filling masterbatch is very high, and masterbatch is well dispersed in main resin, but it has a greater impact on mechanical properties of product and cannot meet better requirements of product.
Since filler masterbatch is mainly used for processing of polyolefin plastic products such as polyethylene or polypropylene, available carrier resins mainly include LDPE, PS, EVA, CPE, etc., but HDPE, PP, and PS are used alone as filler masterbatch for carrier resin production. Strips are brittle and difficult to pelletize (particles are brittle). LLDPE melt flow rate is low and masterbatch produced is not easy to disperse.
Since filler masterbatch is mainly used for processing of polyolefin plastic products such as polyethylene or polypropylene, available carrier resins mainly include LDPE, PS, EVA, CPE, etc., but HDPE, PP, and PS are used alone as filler masterbatch for carrier resin production. Strips are brittle and difficult to pelletize (particles are brittle). LLDPE melt flow rate is low and masterbatch produced is not easy to disperse.
4 ABS plastic vs PVC
ABS plastic can significantly enhance impact strength of PVC, but has no obvious effect on reducing tensile strength. Some varieties also have function of processing aids, and general dosage is 5 to 15 parts. Due to different compositions and relative molecular weights of ABS, modification effects are often different.
5 ABS plastic and MBS plastic
Both ABS plastic and MBS plastic are effective impact modifiers for PVC. Main difference is that the former is mainly used for extruded pipes, profiles and calendering as well as blow molding bottles. It should be noted that such modified polymers have poor weather resistance when blended with PVC because they all contain butadiene unsaturated double bond structures. Light stabilizers should be added to formula. Both have low toxicity and can be used in food contact situations.
6 CPE
CPE generally contains 20% to 50% chlorine, and varieties with a chlorine content greater than 25% are non-flammable. The biggest feature of CPE modified PVC is good weather resistance. It is generally believed that variety with 36% chlorine content has the best modification effect among rigid PVC, can obtain good processability, dispersion and impact resistance; and can also be used as a compatibilizer for PVC and PE blends. For example, adding 15% to 25% of CPE to the PVC/PE/PP blending system (30:28:42) can achieve better blending results.
Varieties containing less than 25% chlorine are not compatible with PVCD. Main disadvantages of CPE are that its products have poor transparency, low tensile strength, and surface gloss of products is not as good as that of pure PVC products. In addition, CPE pellets have higher pores than PVC and contain more gases. During processing, special attention needs to be paid to exhaust. It is best to use an exhaust extruder during extrusion molding.
Varieties containing less than 25% chlorine are not compatible with PVCD. Main disadvantages of CPE are that its products have poor transparency, low tensile strength, and surface gloss of products is not as good as that of pure PVC products. In addition, CPE pellets have higher pores than PVC and contain more gases. During processing, special attention needs to be paid to exhaust. It is best to use an exhaust extruder during extrusion molding.
7 PVC
There are many varieties of PVC due to differences in composition of shell and core, number of layers, etc. For rigid PVC products, it is the most successfully developed transparency (processing or impact) modifier after MBS.
ACR plays following roles in modifying PVC:
a. Improve impact strength of hard PVC materials. As amount of ACR added increases, impact strength of rigid PVC gradually increases, especially in the range of 5 to 10 parts, impact strength changes the fastest, and at 10 parts, it basically reaches peak. After that, increasing amount of ACR has no obvious effect.
b. As amount of ACR added to blend increases, melting and plasticizing time shortens. ACR has effect of promoting gelation and plasticization of PVC resin. PVC with ACR has a significantly increased extrusion expansion than PVC without ACR. General dosage of ACR201 is 1~3 parts.
ACR plays following roles in modifying PVC:
a. Improve impact strength of hard PVC materials. As amount of ACR added increases, impact strength of rigid PVC gradually increases, especially in the range of 5 to 10 parts, impact strength changes the fastest, and at 10 parts, it basically reaches peak. After that, increasing amount of ACR has no obvious effect.
b. As amount of ACR added to blend increases, melting and plasticizing time shortens. ACR has effect of promoting gelation and plasticization of PVC resin. PVC with ACR has a significantly increased extrusion expansion than PVC without ACR. General dosage of ACR201 is 1~3 parts.
8 EVA plastic raw material modified PVC plastic
Varieties of EVA modified plastic PVC are mostly ternary EVA copolymers, such as ethylene-vinyl acetate-carbon oxide (E-VA-CO). Blending compatibility of the two is very good, and it functions as a polymer plasticizer. Because of its excellent durability, it is used in building materials, automobiles, boots and shoes and other industries.
9 PVC plastic and cyanobutadiene rubber (NBR)
PVC plastic has good compatibility with butadiene rubber (NBR), but compatibility between the two is extremely affected by acrylic cyanide (AN) in NBR. When AN content in NBR is about 20%, its blend with PVC has the highest impact strength.
10 PA plastic and PP plastic blending
PA plastics and PP plastics are blended. As compatibilizer increases, mechanical properties of blends improve, indicating that when graft copolymer is added in a large amount within a certain range, chemical reactions at the two interfaces also increase accordingly, compatibility between PA and PP becomes better. However, when graft copolymer exceeds 6.25%, performance decreases.
11 Natural rubber and PE blend
In blending system of natural rubber and PE, due to mutual penetration of amorphous part of PE and amorphous natural rubber interface, mechanical properties are poor. If 6% of the two block copolymers (NR-b-PE) are added, compatibility between the two will be improved, interfacial tension will be reduced, and PE dispersion size will be reduced.
12 Compatibilizer
Amount of compatibilizer should be as little as possible on the premise that it can fully saturate the entire interface of blend. Usual amount is less than 20%.
13 Reactive compatibilizer
Reactive compatibilizers mostly include acid-based, epoxy-based, isocyanate-based, vinyl-based, etc. This type of compatibilizer forms new chemical bonds with blended polymer components and is also called a chemical compatibilizer. It is especially suitable for blending polymers with poor compatibility and easily reactive functional groups.
There are mainly carboxylated PE, carboxylated PP, carboxylated PS, etc., which are designed to promote compatibility between non-polar polymers (PE, PP, PS, etc.) and polar polymer polyamide (PA) .
There are mainly carboxylated PE, carboxylated PP, carboxylated PS, etc., which are designed to promote compatibility between non-polar polymers (PE, PP, PS, etc.) and polar polymer polyamide (PA) .
14 Classification of plastic flame retardant grades
Flame retardant grades of plastics increase step by step from HB, V-2, V-1 to V-0:
HB: The lowest flame retardant rating in UL94 and CSA C22.2 No.0.17 standards. It is required that for samples between 3 and 13 mm thick, burning speed is less than 40 mm per minute; for samples less than 3 mm thick, burning speed is less than 70 mm per minute; or it is extinguished before 100 mm mark.
V-2: After two 10-second burning tests on sample, flame extinguished within 60 seconds. There may be burning objects falling.
V-1: After two 10-second burning tests on sample, flame extinguished within 60 seconds. No burning objects can fall.
V-0: After two 10-second burning tests on sample, flame extinguished within 30 seconds. No burning objects can fall.
HB: The lowest flame retardant rating in UL94 and CSA C22.2 No.0.17 standards. It is required that for samples between 3 and 13 mm thick, burning speed is less than 40 mm per minute; for samples less than 3 mm thick, burning speed is less than 70 mm per minute; or it is extinguished before 100 mm mark.
V-2: After two 10-second burning tests on sample, flame extinguished within 60 seconds. There may be burning objects falling.
V-1: After two 10-second burning tests on sample, flame extinguished within 60 seconds. No burning objects can fall.
V-0: After two 10-second burning tests on sample, flame extinguished within 30 seconds. No burning objects can fall.
15 Some general precautions for dyeing modified plastics
01|PS coloring formula
PS is a colorless and transparent plastic. Its coloring is mainly to make full use of its excellent coloring properties to produce products with various beautiful colors. Vividness, transparency and heat resistance of colorant should be considered. Since general color migrates in the middle of PS, there is a wide range of colorants to choose from.
02|PVC coloring formula
There are several factors that affect coloring of PVC: First, PVC decomposes when heated to release HCL, so a heat stabilizer should be added to formula. Secondly, fillers are often added in order to reduce costs. Types and amounts of these additives have a great impact on color change; thirdly, for soft and hard products, especially the former, adding plasticizer will also cause great changes in color, which should be fully understood and valued.
PS is a colorless and transparent plastic. Its coloring is mainly to make full use of its excellent coloring properties to produce products with various beautiful colors. Vividness, transparency and heat resistance of colorant should be considered. Since general color migrates in the middle of PS, there is a wide range of colorants to choose from.
02|PVC coloring formula
There are several factors that affect coloring of PVC: First, PVC decomposes when heated to release HCL, so a heat stabilizer should be added to formula. Secondly, fillers are often added in order to reduce costs. Types and amounts of these additives have a great impact on color change; thirdly, for soft and hard products, especially the former, adding plasticizer will also cause great changes in color, which should be fully understood and valued.
16 There are some disadvantages in using titanate coupling agent
1. Cost is higher.
2. Due to its own oxidation or interaction with certain antioxidants in polyolefins, titanate can easily form darker compounds, which affects whiteness of calcium carbonate and makes masterbatch gray.
3. For calcium carbonate treated with titanate coupling agent, during storage or processing, lipophilic end of titanate molecule is prone to hydrolysis or alcoholysis and loses its function. Optimal dosage of titanate is determined through experiments based on nature of filler and use of product. In general, recommended dosage is 0.5%-3% of filler.
2. Due to its own oxidation or interaction with certain antioxidants in polyolefins, titanate can easily form darker compounds, which affects whiteness of calcium carbonate and makes masterbatch gray.
3. For calcium carbonate treated with titanate coupling agent, during storage or processing, lipophilic end of titanate molecule is prone to hydrolysis or alcoholysis and loses its function. Optimal dosage of titanate is determined through experiments based on nature of filler and use of product. In general, recommended dosage is 0.5%-3% of filler.
17 Aluminate coupling agent
It can improve dispersion of various fillers and pigments, vividness of pigments. It has a lighter color and can increase organic film of fillers such as calcium carbonate. Thermal stability is better than that of titanate, which can play a chemical role on filler surface and produce adhesion and cross-linking at interface.
Dosage of titanate coupling agent is generally 0.5%~2.5% of filler. For fillers with high specific surface area or high active surface such as carbon black and alumina, dosage can be increased to 1.5%~2.5%. Aluminate coupling agents can be used together with titanate coupling agents to produce synergistic effects, improve performance and reduce costs.
Dosage of titanate coupling agent is generally 0.5%~2.5% of filler. For fillers with high specific surface area or high active surface such as carbon black and alumina, dosage can be increased to 1.5%~2.5%. Aluminate coupling agents can be used together with titanate coupling agents to produce synergistic effects, improve performance and reduce costs.
18 Titanate
Dosage of titanate is calculated as percentage of filler. In process of modifying plastics, optimal dosage should be determined through experiments based on nature of filler and use of product. In general, recommended dosage is 0.5% to 3%.
19 Aluminate
General dosage of aluminate is 0.25~0.5 parts. It can be used together with tribasic lead sulfate and dibasic lead phosphite to play a synergistic stabilizing effect. It also has a certain lubrication effect on PVC and improves surface finish of product. Aluminate coupling agents are cheap and can reduce formula costs, can also be used in PE, PP, PU, PS and other formulas.
20 MBS modified plastic PVC
When using MBS to modify PVC, dosage of MBS is usually maintained at 10% to 15%. And MBS modified PVC is generally a transparent product.
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