The development of PVC stabilizers lot of convenience to our lives , each of R & D will be derived additives affect our lives PVC products , PVC material is polyvinyl chloride , in life can be seen everywhere , making pipe corrosion , pipe fittings, pipelines, pumps black iron oxide and blowers . PVC hard board is widely used in the chemical industry on the production of a variety of tank lining , building corrugated board , doors and windows structure , wall decorations and other construction material . As electrical insulation performance, in electrical and electronic industry, for the manufacture of plugs, sockets , switches and cables. In everyday life , used in the manufacture of PVC sandals, raincoat, toys and artificial leather . These PVC products affect our lives.
Driven by increased demand for PVC products PVC stabilizer which the development of this industry . PVC products affect our lives so PVC stabilizers are increasingly close to the lives of the development of yellow iron oxide life . PVC stabilizer industry development of this industry is also rapid development. Additives trend is towards non-toxic , multifunctional. Complex nature . Molecular technology , formulation auxiliaries and containerization technology progressed rapidly and other characteristics.
Development of stabilizers for PVC additives tend Development of non-toxic non-toxic pollution tends to develop Cd, Pb stabilizers alternatives very active research and development , Ba-Zn, Ca-Zn composite metal such as heat stabilizer and organic tin , organo-antimony stabilizers faster product development , large consumption ; vitamin E is used as the polyolefin "green" antioxidants have been put to practical use , is expected to become a substitute for BHT , Tim Wyatt first developed countries of Ba-Zn, Ca non-toxic and environmentally -Zn stabilizer into the market by the well market reaction.
Multifunctional additives trend
Multifunctional additives variety development has made great progress , antistatic plasticizer , flame retardant plasticizers, stabilizers are versatile products available.
Stabilizers for PVC compound type additives and containerization trend
Synergies between various additives according to the principle of re-dubbed the additive helps assembled in one convenient plastic processing and full automation. Complex products often seen iron oxide black in primary hindered phenolic antioxidants and phosphite antioxidants should month vinegar auxiliary system, and collection of aids wheat is mainly used for PVC processing areas.
Trends molecular weight stabilizers for PVC
Stabilizing additives, plasticizers, flame retardants and other product development progress reflects this trend . In the stabilizing agent , the high molecular weight of 150 hindered amine light stabilizer shows both the effect of thermal oxidation , high molecular weight plasticizer having a resistance out ; molecular weight and the heat resistance and flame retardant resin compatibility obtain improved.
PVC stabilizer future is certainly diversify towards green and healthy environment . Part of our lives .
PVC plasticizer
2013年9月7日星期六
PVC heat stabilizers some of the principles
speaking , those who can improve the thermal stability of the polymer additives are known as heat stabilizers. Because of the poor thermal stability of PVC , so most of the world are used for PVC stabilizer PVC . Therefore , the commonly used stabilizers for PVC means polyvinyl chloride and copolymers of heat stabilizers.
Generally in accordance with the heat stabilizer for panel chemical composition of a heat stabilizer to the classification can be as basic lead salt , a metal soap, organic tin , epoxy compounds, phosphorous esters, polyhydric alcohol. In terms of the role of size can be divided into the main stabilizers for PVC stabilizers and auxiliary stabilizers. Auxiliary stabilizing agent itself or only a small stabilizing effect without thermal stability , but it and the primary stabilizing agent and having a synergistic effect ; primary stabilizer is generally a metal-containing heat stabilizer. And epoxy compounds, phosphites , polyols and other pure compounds are generally used as an auxiliary stabilizer .
As to achieve good stability of PVC often need to use a variety of pvc heat stabilizer , so that some products is titanium dioxide a combination of stabilizers for PVC component complex , a composite stabilizer , such as barium cadmium stabilizer, barium zinc stabilizer etc. , these composite stabilizer usually has joined the PVC processing lubricants and other additives needed to facilitate the users. Many varieties of composite stabilizer with powder, paste , liquid, three forms [ 1 ]
( 1 ) absorption of hydrogen chloride
Me (OOCR) 2 + 2HCl === MeCl2 + 2HOOCR
Wherein Me is : Pb, Ba, Cd, Ca, Zn, Sn, Sb, Mg, Sr , etc.
( 2 ) eliminate the instability of the chlorine atoms substituted or eliminate unstable chlorine atom.
( 3 ) to prevent the auto-oxidation of PVC in the liquid stabilizer hot oxygen and shear stress , easily oxidized by O2 degradation .
( 4 ) metal salts of maleic acid, or to inhibit or eliminate the double bond becomes shorter and less .
Generally in accordance with the heat stabilizer for panel chemical composition of a heat stabilizer to the classification can be as basic lead salt , a metal soap, organic tin , epoxy compounds, phosphorous esters, polyhydric alcohol. In terms of the role of size can be divided into the main stabilizers for PVC stabilizers and auxiliary stabilizers. Auxiliary stabilizing agent itself or only a small stabilizing effect without thermal stability , but it and the primary stabilizing agent and having a synergistic effect ; primary stabilizer is generally a metal-containing heat stabilizer. And epoxy compounds, phosphites , polyols and other pure compounds are generally used as an auxiliary stabilizer .
As to achieve good stability of PVC often need to use a variety of pvc heat stabilizer , so that some products is titanium dioxide a combination of stabilizers for PVC component complex , a composite stabilizer , such as barium cadmium stabilizer, barium zinc stabilizer etc. , these composite stabilizer usually has joined the PVC processing lubricants and other additives needed to facilitate the users. Many varieties of composite stabilizer with powder, paste , liquid, three forms [ 1 ]
( 1 ) absorption of hydrogen chloride
Me (OOCR) 2 + 2HCl === MeCl2 + 2HOOCR
Wherein Me is : Pb, Ba, Cd, Ca, Zn, Sn, Sb, Mg, Sr , etc.
( 2 ) eliminate the instability of the chlorine atoms substituted or eliminate unstable chlorine atom.
( 3 ) to prevent the auto-oxidation of PVC in the liquid stabilizer hot oxygen and shear stress , easily oxidized by O2 degradation .
( 4 ) metal salts of maleic acid, or to inhibit or eliminate the double bond becomes shorter and less .
2013年9月5日星期四
non-toxic PVC heat stabilizer Research
This article describes the mechanism of thermal decomposition of PVC heat stabilizers and mechanism of action . Comprehensive analysis of the types of PVC heat stabilizers and technical status quo ! Pointed out that no heavy metals hydrotalcite ! Rare earth compound heat stabilizer and will become the dominant species .
Polyethylene, polyvinyl chloride PVC is second only to the world 's second-largest synthetic resin azodicarbonamide production over 90,000 , however , PVC there are some difficult to overcome the shortcomings of poor thermal stability which was most prominent. PVC due to poor thermal stability , softening temperature and decomposition temperature difference is small , has caused great difficulties to the process , so the machining process must be a certain amount of heat stabilizer in order to improve its thermal stability. Currently , the largest amount of lead salt heat stabilizer. In building a harmonious society and to ensure sustainable development in mind , people's awareness of environmental protection and health gradually chromium oxide strengthened, therefore , low toxicity , no pollution, has become a complex and efficient PVC heat stabilizers direction of development.
Analysis of the thermal stability of PVC resin
PVC is one of the earliest synthetic thermoplastics , with difficult to burn , good mechanical properties , low prices , abundant source of raw materials , synthetic process maturity and other characteristics, widely used in construction , telecommunications , transportation, electronics, chemicals , packaging and other industries. pvc or subjected to high energy in the heat radiation, such as ultraviolet light "effect occurs under the autocatalytic reaction hcl off , the thermal decomposition mechanism generally believed that there are three kinds . oxygen environment of the free liquid stabilizer radical mechanism ; ( 2 ) under a nitrogen atmosphere ionic mechanism ; ( 3 ) of the single vacuum molecular mechanisms that affect the thermal decomposition pvc chain structure is the main factor , means branched , double, allyl chloride , head structure , and molecular weight conjugated double bonds "in influence ; addition , oxygen , HCL additives and other external factors also have an impact .
Polyethylene, polyvinyl chloride PVC is second only to the world 's second-largest synthetic resin azodicarbonamide production over 90,000 , however , PVC there are some difficult to overcome the shortcomings of poor thermal stability which was most prominent. PVC due to poor thermal stability , softening temperature and decomposition temperature difference is small , has caused great difficulties to the process , so the machining process must be a certain amount of heat stabilizer in order to improve its thermal stability. Currently , the largest amount of lead salt heat stabilizer. In building a harmonious society and to ensure sustainable development in mind , people's awareness of environmental protection and health gradually chromium oxide strengthened, therefore , low toxicity , no pollution, has become a complex and efficient PVC heat stabilizers direction of development.
Analysis of the thermal stability of PVC resin
PVC is one of the earliest synthetic thermoplastics , with difficult to burn , good mechanical properties , low prices , abundant source of raw materials , synthetic process maturity and other characteristics, widely used in construction , telecommunications , transportation, electronics, chemicals , packaging and other industries. pvc or subjected to high energy in the heat radiation, such as ultraviolet light "effect occurs under the autocatalytic reaction hcl off , the thermal decomposition mechanism generally believed that there are three kinds . oxygen environment of the free liquid stabilizer radical mechanism ; ( 2 ) under a nitrogen atmosphere ionic mechanism ; ( 3 ) of the single vacuum molecular mechanisms that affect the thermal decomposition pvc chain structure is the main factor , means branched , double, allyl chloride , head structure , and molecular weight conjugated double bonds "in influence ; addition , oxygen , HCL additives and other external factors also have an impact .
PVC heat stabilizers tribasic lead sulphate process
The first part to introduce the coating amount of tribasic lead sulfate on the thermal stability. Then this one to introduce lead salt concentration of PVC heat stabilizers performance. It can be seen as the lead concentration of the solution ( in PbO dollars) from 300 g / L to 400 g / L, thermal stabilization time from 65 minutes to 72 minutes , followed by an increase as the concentration of thermal stabilization time is no plastic flame retardant longer growing , tends to level up to 500 g / L, which then began to decrease. Pb concentration is too low , inevitably prolonged coating time to affect production capacity , is not conducive to the formation of a good coating layer is too high or if the lead concentration dropped fast , can cause local too thick , the first portion and the second portion respectively, to introduce the PVC heat stabilizers tribasic Lead sulfate process to PVC shoes stabilizer take a factor. This section, to introduce two kinds of factors , they are: the ratio of water and slurry over time effects on the thermal stability ; reaction temperature on the thermal stability of time effects .
First, the ratio of water and slurry over time effects on the thermal stability
Means the ratio of water to an aqueous suspension of the filler in water and the weight ratio of inert filler . Means the black iron oxide ratio of the filler slurry is an aqueous suspension of the water and the weight percent concentration of inert filler .
The following table shows the ratio of water and slurry concentration on the thermal stability of the effect of time can not be uniformly coated on each of inert filler particles , thus affecting the heat stabilizers thermal stabilization time .
First, the ratio of water and slurry over time effects on the thermal stability
Means the ratio of water to an aqueous suspension of the filler in water and the weight ratio of inert filler . Means the black iron oxide ratio of the filler slurry is an aqueous suspension of the water and the weight percent concentration of inert filler .
The following table shows the ratio of water and slurry concentration on the thermal stability of the effect of time can not be uniformly coated on each of inert filler particles , thus affecting the heat stabilizers thermal stabilization time .
2013年9月4日星期三
PVC heat stabilizers Congo test method
PVC used for the final products of different industries. Different performance, PVC heat stabilizers evaluation and testing will need a different approach. Here to introduce a Congo red paper test method.
According to GB GB2917.1-2002, Congo red test method for testing PVC heat stabilizer, a major test method, the one pack stabilizer experimental apparatus shown in Figure 1.
Using an oil bath pot, built glycerin, will be tested PVC heat stabilizers mixed with the material after being loaded into a small test tube, so that the material becomes a slight concussion and firm, and then placed in an oil bath pot among glycerol oil bath pot set in advance a temperature of approximately 170 ℃, PVC material within the small tube and the Stearate zinc upper surface of the upper surface level of glycerin, small tube top, with a thin tube inserted into the plug, the upper and lower transparent glass, the glass tube Congo red paper hit the bottom of the roll inserted so Congo red paper with the lower edge of the upper edge of the PVC material is located about 2 cm. After the start of the experiment, record the test tube to the test tube from Congo red paper turns blue start time is the thermal stabilization time. The basic theory of this experiment is that when the PVC at a temperature of about 170 ℃ when rapid decomposition, but with the addition of a heat stabilizer, suppresses the decomposition, with time, the heat stabilizer consumption occurs when the consumption is completed , PVC dramatically HCl gas decomposition in magnesium hydroxide this case, the test tube as Congo Red reagent reacts easily with HCl and discoloration, will be immediately apparent, a note of the time determined by the length of time to heat stabilizer the effect of pros and cons.
According to GB GB2917.1-2002, Congo red test method for testing PVC heat stabilizer, a major test method, the one pack stabilizer experimental apparatus shown in Figure 1.
Using an oil bath pot, built glycerin, will be tested PVC heat stabilizers mixed with the material after being loaded into a small test tube, so that the material becomes a slight concussion and firm, and then placed in an oil bath pot among glycerol oil bath pot set in advance a temperature of approximately 170 ℃, PVC material within the small tube and the Stearate zinc upper surface of the upper surface level of glycerin, small tube top, with a thin tube inserted into the plug, the upper and lower transparent glass, the glass tube Congo red paper hit the bottom of the roll inserted so Congo red paper with the lower edge of the upper edge of the PVC material is located about 2 cm. After the start of the experiment, record the test tube to the test tube from Congo red paper turns blue start time is the thermal stabilization time. The basic theory of this experiment is that when the PVC at a temperature of about 170 ℃ when rapid decomposition, but with the addition of a heat stabilizer, suppresses the decomposition, with time, the heat stabilizer consumption occurs when the consumption is completed , PVC dramatically HCl gas decomposition in magnesium hydroxide this case, the test tube as Congo Red reagent reacts easily with HCl and discoloration, will be immediately apparent, a note of the time determined by the length of time to heat stabilizer the effect of pros and cons.
stabilizer Synthesis of dimer acid lanthanum
pvc heat stabilizer lanthanum dimer acid synthesis process is as follows:
Instrument
FTS-40 infrared spectrometer, electric oven blast, the contact voltage regulator, vacuum filtration machines, electronic scales, electric mixer, oil bath pot, mortar.
Reagents
PVC resin, PVC-SG5 (China Xinxiang resin plant production); dimer acid, stearic acid, lanthanum oxide, nitric acid, ethanol, sodium hydroxide, glycerol.
Synthesis of dimer antimony trioxide acid lanthanum
Weigh 32. 6 g of La2O3 sample was dissolved in dilute nitric acid, then heated until the reaction is complete and dilute to 250 mL, namely to obtain La (NO3) 3 solution.
A certain amount of NaOH in a beaker, add water, a mixed solvent of ethanol (3:1), to which a certain amount of organic pigments dimer acid, the mixture was stirred at 50 ℃ homogeneous clear solution was obtained, the pH was adjusted to pH9, and then added dropwise La (NO3) 3 solution, stir a few minutes to complete the reaction, filtered after standing in electric blast drying oven spare. First, the product can fully meet the RoHS seven ministries and the state of various types of electronic and electrical products, ban lead and lead limit requirements. Improve titanium dioxide anatase product quality and grades, solve the various policy rules ban on PVC products, lead and environmental requirements. Second, the product can be 100% replacement for lead salt heat stabilizer
Instrument
FTS-40 infrared spectrometer, electric oven blast, the contact voltage regulator, vacuum filtration machines, electronic scales, electric mixer, oil bath pot, mortar.
Reagents
PVC resin, PVC-SG5 (China Xinxiang resin plant production); dimer acid, stearic acid, lanthanum oxide, nitric acid, ethanol, sodium hydroxide, glycerol.
Synthesis of dimer antimony trioxide acid lanthanum
Weigh 32. 6 g of La2O3 sample was dissolved in dilute nitric acid, then heated until the reaction is complete and dilute to 250 mL, namely to obtain La (NO3) 3 solution.
A certain amount of NaOH in a beaker, add water, a mixed solvent of ethanol (3:1), to which a certain amount of organic pigments dimer acid, the mixture was stirred at 50 ℃ homogeneous clear solution was obtained, the pH was adjusted to pH9, and then added dropwise La (NO3) 3 solution, stir a few minutes to complete the reaction, filtered after standing in electric blast drying oven spare. First, the product can fully meet the RoHS seven ministries and the state of various types of electronic and electrical products, ban lead and lead limit requirements. Improve titanium dioxide anatase product quality and grades, solve the various policy rules ban on PVC products, lead and environmental requirements. Second, the product can be 100% replacement for lead salt heat stabilizer
composite stabilizer security of some of the factors
PVC compound stabilizer security should be three aspects to consider, first, the safety of using the processing of raw materials, the second is the user's security and the third is the safety of waste on the PVC processing
aid environment. Processors of security through liquefaction stabilizers, paste technology, granulation and other measures to solve them. , Security protection for the user, can be prepared by a stabilizer or a reactive high molecular weight stabilizers to improve its resistance to pumping, but taking into account the effect of stabilizing the chemical reaction of the molecular level, the above method is not the most appropriate method, the good way to use high security or stabilizers. Stabilizer is selected, the stabilization process must also be considered in the resin and stabilizing agent, or stabilizers react with each other chemicals generated security.
From a variety of security stabilizers see, cadmium stabilizers in the near future will be discontinued. But Impact modifier for PVC a slow process, one of the reasons is that most in the use of cadmium stabilizers when costs are increased by 10% -20%, and cadmium-based stabilizers can not be common to a wide range of PVC compound. Such as processing a narrow range, but also often need to use auxiliary stabilizer compensate for its performance deficiencies. Now cadmium stabilizers performance has reached a performance of cadmium stabilizers. Calcium zinc stabilizers have been developed rapidly. And in powder, paste and liquid, as well as standard-level and non-toxic level for sale, second-generation calcium zinc stabilizer in food and pharmaceutical packaging has been replaced by methyl tin tin and zinc base.
Lead stabilizers set its extraction resistance is small, so the use of security when not a problem, but there are antimony oxide security issues harm the environment. Since lead-based stabilizers, low cost, high efficiency, many companies use this, as non-lead compound stabilizer PVC development, lead salt stabilizer being replaced with non-toxic environment. As many countries ban lead, lead-based stabilizers are withdrawn from the market
In short, the composite heat stabilizer help scale production, lead salt heat stabilizer for the development of a new direction. Compound lead salt stabilizer is an important indicator of the lead content, the current produced by the compound lead salt stabilizer lead content is generally 20% -60%; in the production of PVC plastic window profiles dosage of 3.5-6 parts
From a variety of security stabilizers see, cadmium stabilizers in the near future will be discontinued. But Impact modifier for PVC a slow process, one of the reasons is that most in the use of cadmium stabilizers when costs are increased by 10% -20%, and cadmium-based stabilizers can not be common to a wide range of PVC compound. Such as processing a narrow range, but also often need to use auxiliary stabilizer compensate for its performance deficiencies. Now cadmium stabilizers performance has reached a performance of cadmium stabilizers. Calcium zinc stabilizers have been developed rapidly. And in powder, paste and liquid, as well as standard-level and non-toxic level for sale, second-generation calcium zinc stabilizer in food and pharmaceutical packaging has been replaced by methyl tin tin and zinc base.
Lead stabilizers set its extraction resistance is small, so the use of security when not a problem, but there are antimony oxide security issues harm the environment. Since lead-based stabilizers, low cost, high efficiency, many companies use this, as non-lead compound stabilizer PVC development, lead salt stabilizer being replaced with non-toxic environment. As many countries ban lead, lead-based stabilizers are withdrawn from the market
In short, the composite heat stabilizer help scale production, lead salt heat stabilizer for the development of a new direction. Compound lead salt stabilizer is an important indicator of the lead content, the current produced by the compound lead salt stabilizer lead content is generally 20% -60%; in the production of PVC plastic window profiles dosage of 3.5-6 parts
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